Extraction of hydrocarbons from hydrocarbon-containing materials and/or processing of hydrocarbon-containing materials

ABSTRACT

A method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material includes the steps of providing a first liquid comprising a turpentine liquid; contacting the hydrocarbon-containing material with the turpentine liquid to form an extraction mixture; extracting the hydrocarbon material into the turpentine liquid; and separating the extracted hydrocarbon material from a residual material not extracted.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Divisional of U.S. application Ser. No.13/777,430, filed Feb. 26, 2013, which is a Divisional of U.S.application Ser. No. 12/404,016, filed Mar. 13, 2009 (now U.S. Pat. No.8,404,108), which is a continuation-in-part of U.S. application Ser. No.12/298,993, filed Oct. 29, 2008 (now U.S. Pat. No. 8,404,107), which isa 35 U.S.C. §371 National Phase Entry Application fromPCT/US2008/010831, filed Sep. 17, 2008, and designating the UnitedStates. PCT/US2008/010831 is a Continuation-in-part of U.S. applicationSer. No. 12/174,139, filed Jul. 16, 2008 (now U.S. Pat. No. 8,272,442),and Ser. No. 12/053,126, filed Mar. 21, 2008 (now U.S. Pat. No.8,101,812), and claims the benefit of U.S. Provisional Application No.60/973,964, filed Sep. 20, 2007, each of which is incorporated byreference in their entirety.

FIELD OF THE INVENTION

The present invention relates to the field of extraction of hydrocarbonsfrom hydrocarbon-containing materials.

BACKGROUND OF THE INVENTION

The liquefaction, solubilization and/or extraction of fossil fuels, alsocalled hydrocarbon-containing organic matter, in solid, semi-solid,highly viscous or viscous form (individually and jointly referred to asfossil fuels hereafter) have proven to be extremely challenging anddifficult. As used herein, such fossils fuels include, but are notlimited to, hydrocarbon-containing organic matter within coal, oilshale, tar sands and oil sands (hereinafter jointly called tar sands),as well as crude oil, heavy or extra heavy crude oil, natural gas andpetroleum gas, crude bitumen, kerogen, natural asphalt and/orasphaltene. The difficulty can in part be attributed to the fact thatthese fossil fuels include complex organic polymers linked by oxygen andsulfur bonds, which are often imbedded in the matrices of inorganiccompounds. A need exists to produce additional liquid hydrocarbon feedstock for the manufacture of liquid and gaseous fuels as well as for theproduction of various chemicals, pharmaceuticals and engineeredmaterials as the demand and consumption for hydrocarbon based materialsincreases.

Various technologies or processes have been developed to liquefy,solubilize and/or extract the fossil fuels. None of the prior artliquefaction, solubilization and extraction technologies or processes,however, has proven to be commercially viable on a large scale for alltypes of fossil fuels. This is due to the fact that all of the prior arttechnologies and processes for the liquefaction, solubilization orextraction of hydrocarbons developed to date are expensive to deploy andoperate. Additionally, the prior art processes and technologies for theliquefaction, solubilization and/or extraction of hydrocarbons may bedifficult to scale up, operate and/or control because of one or more ofthe following reasons: (1) operating at an inordinately elevatedpressure; (2) operating at a very high temperature; (3) the need forexpensive processing vessels and equipment that require the externalsupply of hydrogen under extreme conditions; (4) being subjected to amixture, or composition, of two or more reagents, catalysts and/orpromoters, which are frequently highly toxic and are neither renewablenor recyclable; (5) requiring to supply a special form of energy, e.g.,microwave radiation; (6) long process times for partial liquefaction,solubilization or extraction; (7) requiring extraordinarily fineparticles with a size of about 200 mesh (0.074 mm), which is profoundlydifficult and costly to manufacture and handle; and (8) being incapableof recovering and recycling the necessary reagents, catalysts and/orpromoters. Thus, there exists a need to provide additional techniquesand processes for the increased recovery of hydrocarbon materials.

In the past, small-scale experiments have shown that d-limonenesolutions can act as solvents for hydrocarbon-containing materials.However, d-limonene is only partially successful in solubilizinghydrocarbon-containing materials. Further, because d-limonene isextracted from citrus rinds, it is available only in limited quantitiesand at high cost compared with other solvents.

Other solvents used in the past include alkaline solutions andalcohol-water mixtures. These compositions are only marginally usefulfor solubilizing hydrocarbon-containing materials due to the lowsolubility of hydrocarbons in aqueous solutions.

Other prior art methods utilize toluene and/or xylene to re-liquefyparaffin and thick oil to a less viscous material. Such methodsre-liquefy the paraffins using one or more volatile, very dangerous,cancer causing chemicals. These products potentially pollute the groundwater and must be handled with extreme caution as indicated on eachchemical's Material Safety Data Sheet. The paraffin and thick oil revertto their original state once these products have revolatilized causingdeposits in flow lines or storage tank “dropout”.

“Sour” hydrocarbon-containing materials contain greater than about 0.5%sulfur by weight. “Sour” gas contains greater than 4 ppm H₂S and othersulfonated gaseous matter. This sulfur can exist in the form of freeelemental sulfur, hydrogen sulfide gas, and various other sulfurcompounds, including but not limited to, sulfide, disulfides,mercaptans, thiophenes, benzothiophenes, and the like. Each crudematerial or gas may have different amounts or different types of sulfurcompounds, but typically the proportion, complexity and stability of thesulfur compounds are greatest in heavier crude oil fractions. Hydrogensulfide gas is a health hazard because it is poisonous. Further,hydrogen sulfide can react with water to form sulfuric acid, which cancorrode equipment, pipelines, storage tanks, and the like. Thus, it isimportant that those sulfur-containing hydrocarbon-containing materialsthat are reactive be modified to reduce the corrosive effects and toavoid the health risks associated with untreated sulfur-containinghydrocarbon-containing materials.

For primary drilling operations, it would be advantageous to employ aprocess that would enhance solubilization and encourage movement ofadditional or trapped hydrocarbon-containing organic matter that couldthen be recovered allowing existing pressure gradients to force thehydrocarbon-containing organic matter through the borehole. Inparticular, it would be useful to solubilize heavier hydrocarbons thatusually remain in the reservoir through primary drilling operations.

For secondary and tertiary or enhanced oil recovery operations, it wouldbe advantageous to employ a process that would enhance solubilization ofoil to recover hydrocarbon-containing organic matter in the reservoir ina manner that is cost effective and that does not damage the reservoir.While effective methods and compositions exist for tertiary operations,current methods suffer due to expense of operations in comparison to thevalue of the produced hydrocarbon-containing organic matter.

SUMMARY OF INVENTION

In accordance with one embodiment of the present invention, a method ofextracting hydrocarbon-containing organic matter from ahydrocarbon-containing material, includes the steps of providing a firstliquid including a turpentine liquid and contacting thehydrocarbon-containing material with the turpentine liquid such that anextraction mixture is formed, as well as residual material. Theextraction mixture contains at least a portion of thehydrocarbon-containing organic matter and the turpentine liquid. Theresidual material includes non-soluble material from thehydrocarbon-containing material. The residual material can also includea reduced portion of the hydrocarbon-containing organic matter in thecircumstance where all such hydrocarbon-containing material has not beensolubilized by the turpentine liquid and moved into the extractionmixture. The residual material is then separated from the extractionmixture. The extraction mixture is further separated into a firstportion and a second portion. The first portion of the extractionmixture includes a hydrocarbon product stream that includes at least aportion of the hydrocarbon-containing organic matter extracted from thehydrocarbon-containing material. The second portion of the extractionmixture includes at least a portion of the turpentine liquid. In oneembodiment, at least a portion of the turpentine liquid is recycled tothe hydrocarbon-extracting liquid.

In another embodiment, substantially all hydrocarbon-containing organicmatter is extracted into the extraction mixture. In such embodiment, theresidual materials are essentially oil-free and can be further used ordisposed without impact to the environment.

In another embodiment, the present invention provides a method forreducing the rate of or inhibiting the corrosion of a corrodible surfaceor material. During transportation, drilling, downhole operations,exploration, hydrocarbon production, storage, or handling ofhydrocarbon-containing material, for example by pipelines, tankers,casings, fishing tools, or drill bits, the metal surfaces that contactsulfur-containing compounds in the hydrocarbon containing materials maycorrode. By reducing the corrosion rate of the corrodible surfaces,significant cost savings are realized.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic for one embodiment of an apparatus for therecovery of hydrocarbons from tar sands.

FIG. 2 is a schematic for one embodiment of an apparatus for therecovery of hydrocarbons from oil shale.

FIG. 3 is a schematic for one embodiment of an apparatus for therecovery of hydrocarbons from coal.

FIG. 4 is a schematic for the enhanced recovery of hydrocarbons from asubsurface reservoir.

FIG. 5 shows a time course of percentage of bitumen recovery vs. contacttime with various liquids (d-limonene, blend of turpentine liquids, andwater) up to 30 seconds.

FIG. 6 shows the amount of bitumen recovered over a range of Liquid toTar Sands ratios from 1:1 to 6:1 after a 97 second contact time for theblend of turpentine liquids and d-limonene.

FIG. 7 shows the amount of bitumen recovered over a range of Liquid toTar Sands ratios from 1:1 to 6:1 after a 5 minute contact time.

FIG. 8 shows the amount of bitumen recovered over a range of Liquid toTar Sands ratios from 1:1 to 3:1 after a 15 minute contact time.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention relates to a readily deployedcomposition for the extraction, liquefaction and/or solubilization offossil fuels from coal, oil shale, tar sands and the like, as well asfrom reservoirs.

According to one embodiment, a method is provided including the steps ofliquefying, solubilizing and/or extracting hydrocarbon-containingorganic matter from a hydrocarbon-containing material, such as forexample, coal, oil shale, tar sands, or a reservoir containing heavycrude oil, crude oil, natural gas (which frequently coexists with crudeoils and other said fossil fuels), or a combination thereof.Hydrocarbon-containing organic matter includes, but is not limited to,heavy crude oil, crude oil, natural gas, petroleum gas, and the like.Hydrocarbon-containing organic matter can be solid, semi-solid, liquid,sludge, viscous liquid, liquid or gaseous form. Other materials that aresuitable hydrocarbon-containing materials for treatment using the methodof this invention include liquids and solids that includehydrocarbon-containing materials as well as a residual material.Exemplary hydrocarbon-containing materials can also include oil tankbottoms, oil pit or pond sludge and slurry mix, discarded foods, manure,sewage sludge or municipal garbage. Liquefying, solubilizing and/orextracting the hydrocarbon-containing organic matter includes the stepof providing a hydrocarbon-extracting liquid, contacting thehydrocarbon-containing material with the hydrocarbon-extracting liquidso as to extract at least a portion of said hydrocarbon-containingorganic matter from said hydrocarbon-containing material into saidhydrocarbon-extracting liquid to create an extraction mixture thatincludes the hydrocarbon-containing organic matter that has been removedfrom the hydrocarbon-containing material and the hydrocarbon-extractingliquid, and separating the extracted organic matter in thehydrocarbon-extracting liquid from any residual material not extracted.The hydrocarbon-extracting liquid can include an amount of a turpentineliquid, such as for example, terpineol. Turpentine derived from naturalsources generally includes an amount of terpene. In one embodiment, theturpentine liquid includes α-terpineol.

Another embodiment of the invention comprises contacting thehydrocarbon-containing material with a turpentine liquid mixturehereinafter referred to as the blend of turpentine liquids. The blend ofturpentine liquids includes α-terpineol, β-terpineol, β-pinene, andp-cymene. In one embodiment, the multi-component turpentine liquidincludes at least about 30% α-terpineol, and at least about 15%β-terpineol. In another embodiment, the blend of turpentine liquidsincludes about 40-60% α-terpineol, about 30-40% β-terpineol, about 5-20%β-pinene, and about 0-10% p-cymene. In another embodiment, the blend ofturpentine liquids includes about 50% α-terpineol, about 35%β-terpineol, about 10% β-pinene, and about 5% p-cymene. In analternative embodiment, a blend of turpentine liquids includes about40-60% α-terpineol, about 30-40% α-pinene, about 5-20% β-pinene, andabout 0-10% p-cymene. In another embodiment, a blend of turpentineliquids includes about 50% α-terpineol, about 35% α-pinene, about 10%β-pinene, and about 5% p-cymene.

In certain embodiments, the ratio of turpentine liquid tohydrocarbon-containing material is in a range of about 1:2 and 6:1 byweight, or in a range of about 1:2 and 4:1 by weight. In anotherembodiment the ratio of turpentine liquid to hydrocarbon-containingmaterial is in a range of about 1:1 and 3:1 by weight. In embodimentsrelating to reservoir recovery, the ratio can be greater than or equalto about 3:1, and in other embodiments relating to reservoir recoverythe ratio can be greater than or equal to about 4:1. For purposes ofextraction from a reservoir, pore volume is used to determine anestimated measure of the hydrocarbon-containing material. In otheraspects of this invention, such as in the use of tar sands and coal andoil shale, volume of the hydrocarbon-containing material can be moredirectly estimated.

In certain embodiments, the minimum organic matter contained in thehydrocarbon-containing material is greater than or equal to about 1% byweight, in other embodiments greater than or equal to about 10% byweight, and in still further embodiments greater than or equal to about14% by weight of the hydrocarbon-containing material.

Tar sands, coal, oil shale, natural gas, kerogen, bitumen, asphalt, asused herein, can contain as little as about 1% naturally occurringhydrocarbon-containing organic matter. The methods and liquids describedare operable to extract up to about 100% of the hydrocarbon-containingorganic matter from hydrocarbon-containing materials containing very lowto very high amounts of hydrocarbons (i.e., material that includes aslittle as about 1% by weight hydrocarbon material to material thatincludes up to about 100% by weight hydrocarbon material).

In one embodiment of the invention, a liquefaction, solubilization orextraction reagent of choice for the hydrocarbon-containing matter is anatural, synthetic or mineral turpentine, which can include α-terpineol,or be α-terpineol itself.

In certain embodiments, the liquefaction, solubilization and/orextraction of fossil fuels or hydrocarbon-containing organic matter canbe carried out at a temperature within the range of about 2° C. to about300° C. In certain embodiments, the organic matter or material iscontacted with a turpentine liquid at a temperature of less than about300° C., or less than about 60° C. In other embodiments, theliquefaction, solubilization and/or extraction temperatures can bewithin the range of about 20° C. to about 200° C. The pressure underwhich the liquefaction, solubilization and/or extraction of fossil fuelsis to be carried out may typically be within the range of about 1.0×10⁴Pascals (0.1 atm) to about 5.0×10⁶ Pascals (50.0 atm). In certainembodiments, the process can be conducted at a pressure between about5.0×10⁴ Pascals (0.5 atm) to about 8.0×10⁵ Pascals (8.0 atm). In certainother embodiments, the fossil fuels or hydrocarbon-containing organicmatter to be liquefied, solubilized and/or extracted by immersion in, orcontact with, one or more turpentine liquid can be in the form ofparticles, pieces, chunks or blocks of fossil fuels whose sizes arewithin the range of about 0.74 mm to about 10 mm into the interiorportion of a liquefaction, solubilization or extraction vessel(hereafter also referred to as the reactor or contacting vesselinterchangeably) that contains one or more of the said liquefaction,solubilization and/or extraction reagents. In certain embodiments, thesizes of the particles, pieces, chunks or blocks of fossil fuels arewithin the range of about 0.149 mm (100 mesh) to about 20 mm. In certainembodiments, the particles, pieces, chunks or blocks of fossil fuels areagitated by passing the liquefaction, solubilization and/or extractionreagent or reagents in the form of liquid through the particles, pieces,chunks or blocks by boiling the reagent or reagents. In certainembodiments, the duration of liquefaction, solubilization and/orextraction is from about 1 minute to about 90 minutes. The fossil fuelscan be partially or fully liquefied, solubilized and/or extracted; thedegree of liquefaction, solubilization and/or extraction can be effectedby controlling the operating conditions, such as temperature, pressure,intensity of agitation and duration of operation, and/or adjusting thetype, relative amount and concentration of the liquefaction,solubilization or extraction reagent or reagents in the reactor.

The basis of one aspect of the present invention is the unexpecteddiscovery that when about 500 grams of the reagent, α-terpineol, wereadded to about 250 grams of a sample of coal having a particle diameterof less than about 25 mm from the Pittsburgh seam in Washington Countyof Pennsylvania in a tray, the reagent's color turned pitch black almostimmediately, and remained so after several hours. This indicated thatthe color change was not due to the suspension of the coal particles,but rather was indicative of the extraction of hydrocarbon-containingorganic matter from the coal. Subsequently, this 2:1 mixture ofα-terpineol and the coal sample was transferred from the tray to acapped and tightly sealed jar and was maintained under the ambientconditions of about 20° C. and slightly less than about 1.01×10⁵ Pascals(1 atm) for about 25 days. The conversion, (i.e., the degree ofliquefaction), of the coal sample was determined to be about 71 wt. %after filtering, washing with ethanol, drying, and weighing. This 71 wt.% conversion corresponds to nearly all the solubilizable bitumen(organic matter) present in the coal sample whose proximate analyses are2.00 wt. % of as-received moisture, 9.25 wt. % of dry ash, 38.63 wt. %of dry volatile matter, and 50.12 wt. % of dry fixed carbon. A series ofsubsequent experiments with coal, as well as oil shale and tar sandsunder various operating conditions, has shown that the family ofreagents that includes natural and/or synthetic turpentines containingpinenes, and alcohols of pinene, i.e., terpineols, are inordinatelyeffective in liquefying, solubilizing and/or extracting kerogen (organicmatter), bitumen (organic matter) and/or asphaltene (organic matter) inthe fossil fuels, including coal, oil shale, tar sands, heavy crude oiland/or crude oil, without requiring the aid of any catalyst or alkalinemetals. These reagents, except mineral turpentine that is derived frompetroleum, are renewable and “green,” i.e., low in toxicity, andrelatively inexpensive, as compared to all other known liquefaction,solubilization and/or extraction reagents for the fossil fuels, such astetraline, xylene, anthracene, and various solutions or mixtures ofthese reagents with other compounds. Even mineral turpentine derivedfrom petroleum, although not renewable, is relatively low in toxicity,inexpensive, and recyclable. It was also found that any of the saidliquefaction, solubilization and/or extraction reagents penetrates ordiffuses into the particles, pieces, blocks or chunks of fossil fuelsthrough their pores at appreciable rates, thus causing these particles,pieces, chunks or blocks to subsequently release the liquefiable,solubilizable or extractable fraction in them often almost nearlycompletely even under the far milder conditions, e.g., ambienttemperature and pressure, than those required by the recent inventionspertaining to the liquefaction, solubilization and/or extraction of thefossil fuels, such as coal, oil shale, tar sands, crude oil and heavycrude oil.

An aspect of the present invention provides a method of liquefying,solubilizing and/or extracting the fossil fuels orhydrocarbon-containing organic matter from hydrocarbon-containingmaterial, such as coal, oil shale and tar sands, wherein a portion ofsolid or semi-solid fossil fuels is contacted with a turpentine liquidin an extraction mixture, which can be in an absence of an alkali metal,catalyst, hydrogen (H₂) and/or carbon monoxide (CO). While hydrogen andCO can be useful as a mixing agent, one embodiment of the inventionincludes the process and the composition in the absence of hydrogen andCO.

In certain embodiments, the turpentine liquid is selected from naturalturpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, polymersthereof, and mixtures thereof. In certain other embodiments, theturpentine liquid is selected from geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid is selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.

The present invention avoids the environmental, economic, and practicaldisadvantages that have plagued prior extraction systems. To date,solvents comprising various surfactants, surface active agents, alkalineor acidic solutions, salts, volatile organic compounds, and alcoholshave been used with varying degrees of success. However, each of theseknown solvent formulations may have certain drawbacks that one or moreembodiments of the current invention overcome. In one embodiment, therenewable and “green” extraction liquids of the present invention arenaturally derived and substantially surfactant-free. In anotherembodiment, the extraction liquids are surfactant-free. Further, the useof the extraction liquids of the present invention for extractinghydrocarbon-containing organic matter from naturally occurringgeological formations avoids the economic and environmental costsassociated with other known liquefaction, solubilization and/orextraction reagents for fossil fuels.

In certain embodiments, an aspect of the present invention provides amethod for extracting hydrocarbon-containing materials using asubstantially surfactant-free non-aqueous liquid comprising a turpentineliquid. Non-aqueous solvents have the advantage of less leakage into theenvironment, increased extraction of hydrocarbons, avoidance of sulfuricacid formation upon contacting hydrogen sulfide gases and other reactivesulfur compounds trapped within hydrocarbon containing materials,corrosion inhibition, viscosity reduction, and capillary effectelimination.

According to an aspect, solid or semi-solid fossil fuels or otherhydrocarbon-containing materials, such as coal, oil shale, tar sands andheavy crude oil, or for example oil tank bottoms, oil pit or pondsludge, discarded foods, manure, sewage sludge or municipal garbage, maybe provided in any size that facilitates contact with a turpentineliquid. The fossil fuels or hydrocarbon-containing materials can beprovided as particles, pieces, chunks, or blocks, for example, largefragments or pieces of coal or oil shale. According to a certain aspectof the invention, the fossil fuel or hydrocarbon-containing material isprovided as particles. According to a certain aspect of the invention,the particles of fossil fuel or hydrocarbon-containing materials have anaverage particle size of from about 0.01 mm to about 100 mm. In certainother embodiments, the particles of fossil fuel have an average particlesize from about 4 mm to about 25 mm.

According to an aspect of the present invention, a second liquid can beadded to the turpentine liquid. According to a certain aspect of theinvention, the second liquid can be selected from lower aliphaticalcohols, alkanes, aromatics, aliphatic amines, aromatic amines, carbonbisulfide and mixtures thereof. Exemplary mixtures include solventsmanufactured in petroleum refining, such as decant oil, light cycle oiland naphtha, or solvents manufactured in dry distilling coal andfractionating liquefied coal.

As used herein, lower aliphatic alcohols refers to primary, secondaryand tertiary monohydric and polyhydric alcohols of between 2 and 12carbon atoms. As used herein, alkanes refers to straight chain andbranched chain alkanes of between 5 and 22 carbon atoms. As used herein,aromatics refers to monocyclic, heterocyclic and polycyclic compounds.As used herein, aliphatic amines refers to primary, secondary andtertiary amines having alkyl substituents of between 1 and 15 carbonatoms. In certain embodiments, benzene, naphthalene, toluene orcombinations thereof are used. In another embodiment, the loweraliphatic alcohols noted above can be used. In one embodiment thesolvent is selected from ethanol, propanol, isopropanol, butanol,pentane, heptane, hexane, benzene, toluene, xylene, naphthalene,anthracene, tetraline, triethylamine, aniline, carbon bisulfide, andmixtures thereof, at a temperature and pressure operable to maintain thesolvent in liquid form.

In certain embodiments, the ratio of turpentine liquid to any otherturpentine-miscible solvent contained in said fluid is greater than orequal to about 1:1, in certain embodiments greater than or equal toabout 9:4. In certain embodiments, the ratio is greater than or equal toabout 3:1. In yet other embodiments, the ratio is greater than or equalto about 4:1.

According to an aspect of the present invention, the fossil fuel and theturpentine liquid are contacted at a temperature of from about 2° C. toabout 300° C. In certain embodiments, the fossil fuel is contacted bythe turpentine liquid at a temperature of less than about 200° C.

According to a further aspect of the present invention, the fossil fueland the turpentine liquid are contacted at a pressure of from about1.0×10⁴ Pascals (0.1 atm) to about 5.0×10⁶ Pascals (50 atm). Accordingto an aspect, the method is executed at a pressure of from about 0.5 atmto about 8 atm.

According to an aspect of the present invention, the method furtherincludes providing an extraction vessel within which the solid orsemi-solid fossil fuel is contacted with the turpentine liquid.According to an aspect, agitation means can be provided whereby thefossil fuel and the turpentine liquid contained within the reactor orextractor vessel are mixed and agitated.

According to an aspect of the present invention, the fossil fuel andturpentine liquid can be incubated in a holding tank, a pipeline, orother appropriate vessel so as to prolong their contact time. Accordingto a further aspect, the degree of liquefaction, solubilization and/orextraction is controlled by the length of time the solid or semi-solidfossil fuel is in contact with the turpentine liquid and/or thetemperature of the mixture of the fossil fuel and turpentine liquid.

According to an aspect of the present invention, the fossil fuel iscontacted with a heterogeneous liquid including a turpentine liquid andboiling water as an agitant. The bubbling action of boiling water causesagitation thereby increasing the contact surface between the fossil fueland the turpentine liquid. Thus, as a result, a higher degree ofextraction is observed. After extraction, the hydrocarbon-containingturpentine liquid may be separated from water using the difference inliquid densities, e.g. in a settling tank, decanter, or other separationmeans known in the art.

In certain embodiments, the ratio of turpentine fluid to water isgreater than or equal to about 1:1 by volume, to avoid slurry formation,which may render separation of the extracted organic matter in theturpentine liquid-containing fluid difficult.

According to an aspect of the present invention, the fossil fuel iscontacted by the turpentine liquid in the presence of an energy inputselected from thermal energy in excess of about 300° C., pressure inexcess of 50 atm, microwave energy, ultrasonic energy, ionizingradiation energy, mechanical shear-forces, and mixtures thereof.

According to an aspect of the present invention, a liquefaction orsolubilization catalyst is provided to the mixture of fossil fuel andturpentine liquid.

According to an aspect of the present invention, the reaction orsolubilization mixture is supplemented by the addition of a compoundselected from hydrogen, carbon monoxide, water, metal oxides, metals,and mixtures thereof.

According to an aspect of the present invention, a microorganism isincluded in the reaction or solubilization mixture. Select chemicalbonds, for example, sulfur cross-links and oxygen cross-links, in thehydrocarbons of fossil fuels and other hydrocarbon-containing materialsare broken by biotreatment with bacillus-type thermophilic andchemolithotrophic microorganisms selected from naturally occurringisolates derived from hot sulfur springs. The breaking of these selectchemical bonds facilitates the solubilization of hydrocarbons in fossilfuels and other hydrocarbon-containing materials.

In accordance with one embodiment of the present invention, a method isprovided for extracting hydrocarbon-containing organic matter from ahydrocarbon-containing material comprising a viscous liquid, liquid orgaseous fossil fuel material. The method provides a first liquid thatincludes a turpentine liquid. The turpentine liquid is contacted withthe hydrocarbon-containing material in-situ in an underground formationcontaining said fossil fuel material, thereby forming an extractionmixture so as to extract hydrocarbon-containing organic matter into saidturpentine liquid and form an extraction liquid. The extraction liquidis removed from said formation, wherein the extraction liquid includesthe turpentine liquid containing the extracted hydrocarbon-containingorganic matter. The extracted hydrocarbon-containing organic matter isseparated from a residual material not extracted. The method can furtherinclude separating said extracted hydrocarbon-containing organicmaterial from the turpentine liquid. The viscous liquid, liquid orgaseous fossil fuel material can be heavy crude oil, crude oil, naturalgas, or a combination thereof. The underground formation may be a crudeoil reservoir or a natural gas reservoir, for example.

The present invention can be deployed readily in-situ to liquefy and/orsolubilize directly the fossil fuels in underground formations, andextract the resulting liquid products from such formations.

An exemplary extraction reagent of the present invention may be a fluid,e.g. a liquid, which may have a very strong physicochemical affinitywith bituminous organic matter, including bitumen, kerogen and/or tar,in coal, oil shale and tar sands. When the extraction reagent of thepresent invention and bituminous organic matter comprising mainlyhydrocarbons come into direct contact with each other, the organicmatter is extracted into the extraction reagent of the presentinvention, thereby liquefying the organic matter. Upon contact, thehydrocarbons and the extraction reagent of the present invention rapidlyform a homogeneous solution, i.e., a one-phase liquid.

It is possible to take advantage of the physicochemical affinity betweenthe extraction reagent of the present invention and the bituminousmatter for enhancing oil recovery from oil reservoirs under in-situconditions. The prior art in-situ recovery techniques applied to-date inoil reservoirs resort mostly to the so-called frontal displacementmethod. This process is strictly controlled by the characteristics ofthe multi-phase fluid flow in a porous medium. This tends to leave alarge portion, often exceeding about 40% of the original oil,unrecovered from the formation, even for the “good” low viscosity oilreservoirs. The extraction reagent of the present invention enhances oilrecovery by overcoming the complex behavior of prior multi-phase flowtechniques prevailing under in-situ conditions.

The present invention provides an improved method for increasingflowability and extraction of viscous or immobile hydrocarbon containingmaterials by contacting a hydrocarbon-containing material with aturpentine liquid, which decreases the viscosity of thehydrocarbon-containing material. Flow is also enhanced by thenon-aqueous nature of the turpentine liquid due to elimination of thecapillary effect associated with aqueous solutions. Contacting can takeplace in situ or ex situ.

The present invention takes advantage of the very strongphysico-chemical affinity of the turpentine liquid.

One method of the present invention injects an extraction reagent of thepresent invention into an oil or natural gas reservoir through aninjection well.

Oil is extracted into the extraction reagent of the present inventionwhen the two come into contact in an oil reservoir, thereby yielding ahomogeneous solution, i.e., a one-phase liquid. The extraction reagentof the present invention does not simply displace the oil as it travelsfrom the injection well to a production well in fluid communication withan underground formation. Rather, extraction of previously trapped oilinto the extraction reagent of the present invention continues until theextraction reagent is completely exhausted in forming the homogeneoussolution with oil. Thereafter, this homogeneous solution that includesthe extracted hydrocarbons then simply flows through the pores of thereservoir as a one-phase liquid, eventually reaching a production well.

The following examples illustrate three specific embodiments of in-situmethods for oil recovery of the present invention.

In a first in-situ embodiment, between about three (3.0) to seven (7.0)pore volumes of an extraction reagent of the present invention areinjected into an oil reservoir that has previously been water-flooded tothe residual oil saturation while producing about 51% of the originaloil in the reservoir. The subsequent injection of the extraction reagentcan unexpectedly produce about an additional 41% of the original oil inthe reservoir. This embodiment of the method was experimentallyvalidated, as described in Example 22 herein below.

In a second in-situ embodiment, between about two (2.0) to five (5.0)pore volumes of an extraction reagent of the present invention areinjected into an oil reservoir. At the outset, injection of theextraction reagent causes only oil to be produced until about one-third(0.3) to three-quarter (0.75) of pore volume of the extraction reagentof the present invention is injected; thereafter, the extraction reagentof the present invention into which oil has been extracted, is produced.The majority of the oil present can be recovered upon injecting betweenabout one and a half (1.5) to three and a half (3.5) total pore volumesof the reagent. The method unexpectedly recovers about 90% of theoriginal oil in the reservoir. This embodiment of the method also isexperimentally validated, as described in Example 22 herein below.

In a third in-situ embodiment, an extraction reagent of the presentinvention is injected to improve the oil recovery from oil reservoirscontaining very viscous oil, e.g., the reservoirs of the “Orinoco OilBelt” in Venezuela. The recovery factor for extra heavy oil with priorart recovery methods is low, typically ranging from about 10% to about15% of the original oil in such reservoirs. The unexpected increase inthe recovery efficiency from these reservoirs with injection of theturpentine liquid extraction reagent of the present invention can befurther enhanced by adopting horizontal wells for both production andinjection wells, and periodic steam soaking of these wells.

Ultimate recovery of natural gas from a large gas reservoir can beincreased with the injection of an extraction reagent of the presentinvention into a reservoir. The gas production from such a reservoiroften creates dangerously large-scale subsidence on the surfaces of thegas field, e.g., the “Groeningen” field in the Netherlands. As such, itis frequently necessary that the reservoir pressure be maintained bywater injection. Water injected into the reservoir can trap up to about30% of the gas in-situ at high pressure due to the two-phase flow ofwater and gas through the reservoir with a low permeability. With theinjection of an extraction reagent of the present invention, however,the trapped gas in the reservoir is extracted into the reagent and flowsto the production wells. By separating the reagent and gas at thesurface, the gas is recovered and the reagent is recycled for reuse.

The extraction methods of the present invention can be implemented afterone or more of the known methods for facilitating oil production, e.g.,CO₂ or natural gas injection and surfactant addition, are executed.

Still other aspects and advantages of the present invention will becomeeasily apparent by those skilled in the art from this description,wherein certain embodiments of the invention are shown and describedsimply by way of illustration of the best mode contemplated of carryingout the invention. As will be realized, the invention is capable ofother and different embodiments, and its several details are capable ofmodifications in various obvious respects, without departing from theinvention. Accordingly, the description is to be regarded asillustrative in nature and not as restrictive.

EXEMPLARY EMBODIMENTS FOR CARRYING OUT THE INVENTION

Coal

In certain embodiments, anthracite or bituminous coal can be ground tosizes ranging from about 0.841 mm (20 mesh) to about 0.149 mm (100mesh), and subsequently be solubilized and/or extracted, i.e.,liquefied, by immersing in a turpentine liquid under a pressure withinthe range of about 1.0×10⁵ Pascals (1 atm) to about 2.0×10⁵ Pascals (2.0atm). In certain other embodiments, the turpentine liquid can benatural, synthetic or mineral turpentine that includes up to about 50-70volume % of α-terpineol, about 20-40 volume % of β-terpineol, and about10 volume % of other components. As defined herein, the term “othercomponents” can include natural turpentine, synthetic turpentine,mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol,β-terpineol, γ-terpineol, terpene resins, α-terpene, β-terpene,γ-terpene, and mixtures thereof. In other embodiments, the turpentineliquid can include at least one compound selected from geraniol,3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinanehydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol,p-menthan-8-ol, α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In yet otherembodiments, the turpentine liquid can include at least one compoundselected from anethole, camphene; p-cymene, anisaldeyde,3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene, alloocimene,alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor,citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid,cintronellal, menthone, and/or mixtures thereof. In certain embodiments,the bed of ground anthracite or bituminous coal can be agitated bypassing said turpentine liquid at a temperature in the range between 80°C. and about 130° C., or possibly up to the boiling point of saidturpentine liquid. In certain other embodiments, the duration ofsolubilization and/or extraction, i.e., liquefaction, can be withinabout 10 minutes to about 40 minutes. In certain embodiments, thecontact time for the extraction of hydrocarbon-containing organic matterfrom coal is less than about 5 minutes.

In some embodiments, lignite, brown coal, or any other low-rank coalscan be ground to sizes ranging from about 0.419 mm (40 mesh) to about0.074 mm (200 mesh), and subsequently be solubilized and/or extracted,i.e., liquefied, by immersing in a turpentine liquid under a pressurewithin the range of about 1.0×10⁵ Pascals (1 atm) to about 2.0×10⁵Pascals (2.0 atm). In certain other embodiments, the turpentine liquidcan be natural, synthetic or mineral turpentine that includes about70-90 volume % of α-terpineol, about 5-25 volume % of β-terpineol, andabout 5 volume % of other components. In other embodiments, the bed ofground lignite, brown coal, or any other low-rank coals can be agitatedby passing said turpentine liquid at a temperature in the range betweenabout 80° C. and about 130° C., or possibly up to the boiling point ofsaid turpentine liquid. In certain other embodiments, the solubilizationand/or extraction, i.e., liquefaction, can be within about 20 minutes toabout 60 minutes. In certain embodiments, the contact time for theextraction of hydrocarbon-containing organic matter from coal is lessthan about 5 minutes.

Oil Shale

In certain embodiments, oil shale can be ground to sizes ranging fromabout 0.419 mm (40 mesh) to 0.074 mm (200 mesh), and subsequently besolubilized and/or extracted, i.e., liquefied, by immersing in aturpentine liquid under a pressure within the range of about 1.0×1.0⁵Pascals (1 atm) to about 2.0×10⁵ Pascals (2.0 atm). In otherembodiments, the turpentine liquid can be natural, synthetic or mineralturpentine that includes about 70-90 volume % of α-terpineol, about 5-25volume % of β-terpineol, and about 5 volume % of other components. Incertain other embodiments, the bed of ground oil shale can be agitatedby passing said turpentine liquid at a temperature in the range betweenabout 80° C. and about 130° C., or possibly up to the boiling point ofsaid turpentine liquid. In other embodiments, the solubilization and/orextraction, i.e., liquefaction, can be within about 30 minutes to about60 minutes. In certain embodiments, the contact time for the extractionof hydrocarbon-containing organic matter from oil shale is less than 5minutes.

Tar Sands

In certain embodiments, tar sands can be broken up to sizes ranging fromabout 25.4 mm (1 mesh) to 4.76 mm (4 mesh), and subsequently besolubilized and/or extracted, i.e., liquefied, by immersing in aturpentine liquid under a pressure within the range of about 1.0×1.0⁵Pascals (1 atm) to about 2.0×10⁵ Pascals (2.0 atm). In otherembodiments, the turpentine liquid can be natural, synthetic or mineralthat includes containing about 40-60 volume % of α-terpineol, about30-50 volume % of β-terpineol, about 5 volume % of α and/or β-pinene andabout 5 volume % of other components. In another embodiment, a bed ofground oil shale can be agitated by passing said turpentine liquid at atemperature in the range between about 60° C. and about 90° C., orpossibly up to the boiling point of said turpentine liquid. In otherembodiments, the solubilization and/or extraction, i.e., liquefaction,can be within about 10 minutes to about 30 minutes. In certainembodiments, the contact time for the extraction ofhydrocarbon-containing organic matter from tar sands is less than 5minutes.

Crude Oil

In certain embodiments, light and medium crude oil can be produced insitu, i.e., removed from an underground reservoir, for primary,secondary or tertiary recovery, by injecting about one (1.0) to aboutfive (5.0) pore volumes of a turpentine liquid. In other embodiments,between about two (2.0) and about four (4.0) pore volumes of aturpentine liquid can be injected. In certain embodiments, theturpentine liquid can be natural, synthetic or mineral turpentine thatincludes about 40-70 volume % of α-terpineol, about 30-40 volume % ofβ-terpineol, about 10 volume % of α and/or β-pinene and about 10 volume% of other components. In certain embodiments, the injection of aturpentine liquid can be followed by waterflooding with about one (1.0)to about three (3.0) pore volumes of water.

In certain embodiments, heavy and extra heavy crude oil can be producedin situ, i.e., removed from an underground reservoir, for primary,secondary or tertiary recovery, by injecting about one (1.0) to aboutfive (5.0) pore volumes of a turpentine liquid. In other embodiments,between about two (2.0) and about four (4.0) pore volumes of aturpentine liquid can be injected. In certain embodiments, theturpentine liquid can be natural, synthetic or mineral turpentine thatincludes about 50-70 volume % of α-terpineol, about 20-35 volume % ofβ-terpineol, about 10 volume % of α and/or β-pinene and about 5 volume %of other components. In other embodiments, the method can be used inconjunction with steam injection prior to, during, or after injection ofthe hydrocarbon-extracting liquids.

Referring to FIG. 1, an apparatus for the recovery ofhydrocarbon-containing organic matter from tar sands is provided.Apparatus 100 includes turpentine liquid supply 102, which canoptionally be coupled to a pump 104, to supply a turpentine liquid tocontacting vessel or extraction vessel 110. In certain embodiments, theturpentine liquid supply can include means for heating the turpentineliquid. In certain embodiments, the contacting vessel can be an inclinedrotary filter or trommel. Tar sands sample 106 is provided to conveyor108 or like feeding apparatus for supplying the tar sands to an inlet ofcontacting vessel 110. Optionally, conveyor 108 can include a filterscreen or like separating apparatus to prevent large particles frombeing introduced into the process. Contacting vessel 110 includes atleast one inlet for turpentine liquid to be introduced and contactedwith the tar sands. Contacting vessel 110 can include a plurality oftrays or fins 114 designed to retain the tar sands in the contactingvessel for a specified amount of time, and to increase or controlcontact between the tar sands particles and the turpentine liquid. Incertain embodiments, the contacting vessel can be an inclined rotaryfilter. An extraction mixture that includes the extracting liquid andhydrocarbon-containing organic matter extracted from the tar sands isremoved from contacting vessel 110 via outlet 116, which can includefilter 118 to prevent the removal of solids with the extraction mixturethat includes the extracted hydrocarbon-containing organic matter. Pump120 can be coupled to outlet 116 to assist with supplying the extractionmixture to holding tank 122. Line 124 can be coupled to holding tank 112for supplying the extraction mixture for further processing. Afterextraction of the hydrocarbon-containing organic matter, inorganicsolids and other materials not soluble in the turpentine liquid can beremoved from the contacting vessel via second conveyor 126. Turpentineliquids operable for the recovery of hydrocarbons from tar sandsutilizing apparatus 100 can include, but are not limited to, liquidsthat include α-terpineol and β-terpineol.

Referring now to FIG. 2, apparatus 200 is provided for the recovery ofhydrocarbon-containing organic matter from oil shale and othersedimentary rock formations that include recoverable hydrocarbonmaterials. Oil shale sample 202 is supplied to grinder or crusher 204 toreduce the size of the oil shale. In one embodiment, grinder or crusher204 reduces the oil shale to between about 0.074 and 0.42 mm indiameter. Crushed oil shale may optionally be supplied to a filter toensure uniform and/or conforming particle size. First conveyor 206provides particles from grinder or crusher 204 to contacting vessel 208.Contacting vessel 208 is coupled to turpentine liquid supply 210, whichmay optionally be coupled to a pump, and which supplies a turpentineliquid to at least one inlet 212 coupled to contacting vessel 208. Incertain embodiments, the turpentine liquid supply can include means forheating the turpentine liquid. Contacting vessel 208 can include aplurality of trays or fins 214 designed to retain the tar sands in thecontacting vessel for a specified amount of time, and to increase orcontrol contact between the tar sands particles and the turpentineliquid. In certain embodiments, the contacting vessel can be an inclinedrotary filter or trommel. An extraction mixture stream that includes theturpentine liquid and recovered hydrocarbon-containing organic matterfrom the oil shale is collected via outlet 216 and supplied to holdingtank 220. Pump 218 is optionally coupled to outlet 216 to assist withthe supply of the extraction mixture stream to holding tank 220. Theextraction mixture stream can be coupled to line 222 for supplying theextraction mixture stream to further processing. Second conveyor 224assists with the removal of inorganic or insoluble materials fromcontacting vessel 208. Turpentine liquids operable for the recovery ofhydrocarbons from oil shale utilizing apparatus 200 can include, but arenot limited to, α-terpineol and β-terpineol.

Referring now to FIG. 3, apparatus 300 is provided for the recovery ofhydrocarbon-containing organic matter from coal. Coal sample 302 issupplied to grinder or crusher 304 to reduce the size of the coal. Inone embodiment, grinder or crusher 304 reduces the coal to between about0.01 and 1 mm in diameter, depending upon the quality of the coalsample. In certain embodiments, the grinder or crusher 304 can be a wetgrinder. Crushed coal may optionally be supplied to a filter to ensureuniform and/or conforming particle size. Crushed coal is supplied tofirst contacting vessel 306. First contacting vessel 306 is also coupledto a turpentine liquid supply 308, which may optionally be coupled topump 310, and which supplies the turpentine liquid to first contactingvessel 306. In certain embodiments, the turpentine liquid supply caninclude means for heating the turpentine liquid. First contacting vessel306 includes mixing means 312 designed to agitate and improve or controlcontact between the solid coal particles and the turpentine liquid. Anextraction mixture stream that includes the turpentine liquid andrecovered hydrocarbon-containing organic matter from the oil shale iscollected via first contacting vessel outlet 313 and supplied to secondcontacting vessel 316. Pump 314 is optionally coupled to outlet 313 toassist with the supply of the extraction mixture stream to the secondcontacting vessel 316. Second contacting vessel 316 can include a seriesof trays or fins 318 designed to increase or control separation of thesolids and turpentine liquids. Optionally, the second contacting vessel316 can be an inclined rotary filter or trommel. The extraction mixturestream can be collected from second contacting vessel outlet 320, whichmay optionally be coupled to pump 322, to assist with supply of theextraction mixture stream to holding tank 324. Liquid coal and anyturpentine liquid present in holding tank 324 can be supplied to aliquid coal refinery or other processing step via line 326. Conveyor 328can be coupled to second contacting vessel 316 for removal and recoveryof the solids as a by-product of the process. Turpentine liquidsoperable for the recovery of hydrocarbons from coal utilizing apparatus300 can include, but are not limited to, α-terpineol and β-terpineol.The apparatus 300 can also be used to process high and low grade oilshale.

Referring now to FIG. 4, process 400 is provided for the enhancedrecovery of hydrocarbon-containing organic matter from ahydrocarbon-containing subsurface formation. Hydrocarbon-containingreservoir 404 is shown positioned below the surface 402. Producer well406 is already in operation. Injection well 408 is provided for theinjection of a turpentine liquid via line 410. The turpentine liquidfacilitates the liquefaction, solubilization and/or extraction ofhydrocarbon-containing organic matter present in the reservoir, as wellas providing the driving force to push the hydrocarbon-containingorganic matter in the formation toward the producer well. A hydrocarbonproduct stream that includes injected turpentine liquid is collected vialine 412. Turpentine liquids operable for the recovery of hydrocarbonsfrom a hydrocarbon-containing subsurface formation utilizing apparatus400 can include, but are not limited to, α-terpineol and β-terpineol.

In certain embodiments, the turpentine liquid for increasing productionfrom an oil well is provided that includes at least about 30% by volumeof natural turpentine, synthetic turpentine, mineral turpentine, pineoil, α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In otherembodiments, the turpentine liquid includes at least about 30% by volumegeraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,isoborneol, p-menthan-8-ol, α-terpinyl acetate, citronellol,p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, ormixtures thereof. In yet other embodiments, the turpentine liquidincludes at least about 30% by volume anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, or mixtures thereof.

In certain embodiments, the turpentine liquid includes at least about40% by volume α-terpineol. In other embodiments, the turpentine liquidincludes at least about 25% by volume β-terpineol. In yet otherembodiments, the turpentine liquid includes at least about 40% by volumeα-terpineol and at least about 25% by volume β-terpineol. In otherembodiments, the turpentine liquid includes at least about 50%α-terpineol, and in certain embodiments also includes β-terpineol. Incertain embodiments, the turpentine liquid includes at least about 20%by volume of β-terpineol. In certain embodiments, the turpentine liquidincludes between about 50 and 70% by volume of α-terpineol and betweenabout 10 and 40% by volume of β-terpineol.

In another aspect, a process for increasing production from asub-surface hydrocarbon-containing reservoir undergoing enhancedrecovery operations is provided that includes injecting a turpentineliquid into the reservoir through an injection well to stimulateproduction of the hydrocarbon-containing material. The turpentine liquidcan include at least one compound selected from natural turpentine,synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, and mixtures thereof. In other embodiments, theturpentine liquid can include at least one compound selected fromgeraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,isoborneol, p-menthan-8-ol, α-terpinyl acetate, citronellol,p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, andmixtures thereof. In yet other embodiments, the turpentine liquid caninclude at least one compound selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof. A hydrocarbon-containing organic matterproduction stream that includes the turpentine liquid and recoveredhydrocarbons is recovered from a producer well associated with thehydrocarbon-containing reservoir. The hydrocarbon-containing organicmatter production stream can be separated into a recovered hydrocarbonsstream and a turpentine liquid for recycle. In certain embodiments, themethod can further include the step of injecting the turpentine liquidrecycle stream into the injection well.

In another aspect, a method for recovering hydrocarbon-containingorganic matter from hydrocarbon-containing coal rich sub-surfaceformation is provided. The method includes the steps of extracting thehydrocarbon-containing organic matter by a process consistingessentially of the steps of obtaining coal sample that includes arecoverable hydrocarbon-containing organic matter and grinding the coalto produce crushed coal. The crushed coal is filtered and fed to acontacting vessel that includes at least one inlet for supplying ahydrocarbon extracting liquid to the contacting vessel. The crushed coalis contacted with a substantially surfactant-free non-aqueoushydrocarbon-extracting liquid consisting essentially of a turpentineliquid selected from the group consisting of natural turpentine,synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof, such that an extraction mixture isformed and a residual material is formed. The extraction mixtureincludes at least a portion of the hydrocarbon-containing organic matterin the turpentine liquid, and the residual material includes at least aportion of non-soluble material from the coal that is not soluble in theturpentine liquids. The residual material is separated from theextraction mixture, and the hydrocarbon-containing material organicmatter is separated from the turpentine liquid to produce a hydrocarbonproduct stream and a turpentine liquid stream, wherein the hydrocarbonproduct stream includes at least a portion of the hydrocarbon-containingorganic matter from the coal. At least a portion of the turpentineliquid stream is recycled to the contacting step.

In another aspect, a method for increasing production from ahydrocarbon-containing sub-surface hydrocarbon formation undergoingenhanced recovery operations is provided. The method includes the stepsof injecting a turpentine liquid into the formation through an injectionwell. In certain embodiments, the turpentine liquid includes at leastabout 40% by volume α-terpineol and at least about 10% by volumeβ-terpineol. The turpentine liquid solubilizes, extracts and/ordisplaces the hydrocarbon-containing materials from the formation, whichare subsequently recovered from the formation with the turpentine liquidthrough a producer well. In certain embodiments, the method furtherincludes separating the hydrocarbons from the turpentine liquid. In yetother embodiments, the method further includes recycling the turpentineliquid to the injection well. In certain embodiments, α-terpineol ispresent in an amount between about 40 and 70% by volume. In certainother embodiments, α-terpineol is present in an amount of at least about70% by volume. In yet other embodiments, β-terpineol is present in anamount between about 10 and 40% by volume. In other embodiments, theturpentine liquid further includes up to about 10% by volumeγ-terpineol. In other embodiments, the turpentine liquid can include upto about 25% by volume of an organic solvent selected from methanol,ethanol, propanol, toluene and xylenes. The method is useful for therecovery of hydrocarbon-containing organic matter during primary,secondary and tertiary recovery operations, including after secondaryrecovery operations that include waterflooding.

In another aspect, a turpentine liquid for the recovery ofhydrocarbon-containing organic matter from tar sands is provided. In oneembodiment, the turpentine liquid includes at least about 30% by volumeα-terpineol and at least about 25% by volume β-terpineol. In anotherembodiment, the turpentine liquid includes between about 30 and 70% byvolume α-terpineol, between about 25 and 55% by volume β-terpineol, upto about 10% by volume α-terpene, and up to about 10% by volumeβ-terpene.

In another aspect, a turpentine liquid for recoveringhydrocarbon-containing organic matter from high grade coal sources, suchas for example, anthracite or bituminous coal, is provided. In oneembodiment, the turpentine liquid includes at least about 45% by volumeα-terpineol and at least about 15% by volume β-terpineol. In anotherembodiment, the turpentine liquid includes between about 45 and 80% byvolume α-terpineol, between about 15 and 45% by volume β-terpineol, upto about 10% by volume α-terpene, and up to about 10% by volumeβ-terpene.

In another aspect, a turpentine liquid for recoveringhydrocarbon-containing organic matter from low grade coal sources isprovided. In one embodiment, the turpentine liquid includes at leastabout 60% by volume α-terpineol and up to about 30% by volumeβ-terpineol. In another embodiment, the turpentine liquid includesbetween about 60 and 95% by volume α-terpineol, up to about 30% byvolume β-terpineol, up to about 5% by volume α-terpene, and up to about5% by volume β-terpene.

In another aspect, a turpentine liquid for recoveringhydrocarbon-containing organic matter from oil shale is provided. Asused herein, oil shale generally refers to any sedimentary rock thatcontains bituminous materials. In one embodiment, the turpentine liquidincludes at least about 60% by volume α-terpineol and up to about 30% byvolume β-terpineol. In another embodiment, the turpentine liquidincludes between about 60 and 95% by volume α-terpineol, up to about 30%by volume β-terpineol, up to about 5% by volume α-terpene, and up toabout 5% by volume β-terpene.

In another aspect, a turpentine liquid is provided for recoveringhydrocarbon-containing organic matter from light and medium crude oil.In one embodiment, the turpentine liquid includes at least between about40 and 70% by volume α-terpineol and at least between about 30 and 40%by volume β-terpineol. In yet another embodiment, the turpentine liquidincludes between about 40 and 70% by volume α-terpineol, between about30 and 40% by volume β-terpineol, up to about 10% by volume α-terpene,and up to about 10% by volume β-terpene.

In another aspect, a turpentine liquid is provided for recoveringhydrocarbon-containing organic matter from heavy and extra heavy crudeoil. In one embodiment, the turpentine liquid includes at least betweenabout 50 and 70% by volume α-terpineol and at least between about 30 and40% by volume β-terpineol. In another embodiment, the turpentine liquidincludes between about 50 and 70% by volume α-terpineol, between about30 and 40% by volume β-terpineol, up to about 10% by volume α-terpene,and up to about 10% by volume β-terpene.

In another aspect, a method for recovering hydrocarbon-containingorganic matter from tar sands is provided. The method includes obtaininga tar sand sample, such as for examply, by mining a formation rich intar sands to provide a tar sands sample, wherein the tar sands sampleincludes a recoverable hydrocarbon-containing organic matter andresidual inorganic or insoluble material. The tar sands sample issupplied to a contacting vessel, wherein the contacting vessel includesat least one inlet for supplying a hydrocarbon-extracting liquid thatconsists essentially of a turpentine liquid for recovery of hydrocarbonsfrom the tar sands. The tar sands sample is contacted with ahydrocarbon-extracting liquid and agitated to extract thehydrocarbon-containing organic matter from the tar sands to produce aresidual material and an extraction mixture. The extraction mixtureincludes the hydrocarbon-extracting liquid and recoveredhydrocarbon-containing organic matter, and the residual material whichincludes at least a portion of the non soluble material. The extractionmixture is separated from the residual material, and is furtherseparated into a hydrocarbon product stream and a hydrocarbon-extractingliquid stream, wherein the hydrocarbon-extracting liquid stream includesat least a portion of the hydrocarbon-containing organic matterextracted from the tar sands. In certain embodiments, the method furtherincludes the step of recycling the turpentine liquid stream to thecontracting vessel. In other embodiments, the extraction mixture can beseparated by distillation to produce the hydrocarbon product stream andthe turpentine liquid recycle stream.

In certain embodiments, the turpentine liquid can include α-terpineol.In other embodiments, the turpentine liquid can include at least about40% by volume α-terpineol and between about 10 and 40% by volumeβ-terpineol. In certain embodiments, between about 0.5 and 4 equivalentsof the turpentine liquid is used to contact the tar sands and recoverhydrocarbons. In certain embodiments, between about 0.5 and 2.0equivalents of the turpentine liquid is used to contact the tar sandsand recover hydrocarbons.

In another aspect, a method for recovering hydrocarbon-containingorganic matter from a hydrocarbon rich oil shale is provided. The methodincludes mining a rock formation that includes hydrocarbon-containingorganic matter to produce a hydrocarbon containing oil shale thatincludes a recoverable hydrocarbon material and inorganic or insolublematerial. The oil shale is ground to produce comminutedhydrocarbon-containing oil shale. The comminuted hydrocarbon-containingoil shale is then filtered with a filter screen to prevent or controlthe excessively large particles from being supplied to the extractionprocess. The comminuted hydrocarbon-containing oil shale is fed to acontacting vessel, wherein the contacting vessel includes at least oneinlet for supplying a hydrocarbon-extracting liquid consistingessentially of a turpentine liquid for recovery of hydrocarbons from thecrushed hydrocarbon-containing oil shale. The comminutedhydrocarbon-containing oil shale is contacted with thehydrocarbon-extracting liquid such that an extraction mixture is formedand a residual material is formed, wherein the extraction mixtureincludes at least a portion of the hydrocarbon-containing organic matterin the hydrocarbon-extracting solvent and the residual material includesat least a portion of the non-soluble material from the oil shale. Theextraction mixture is separated from the residual material. Thehydrocarbon-containing organic matter from the hydrocarbon-extractingliquid in the extraction mixture are separated from the turpentineliquid to produce a hydrocarbon product stream that includes at least aportion of the hydrocarbon-containing organic matter and ahydrocarbon-extracting liquid stream. In certain embodiments, theturpentine liquid stream is recycled to the contacting vessel. In otherembodiments, the comminuted hydrocarbon-containing oil shale has a meanparticle size of less than about 0.4 mm in diameter. In otherembodiments of the method for the recovery of hydrocarbon-containingorganic matter from oil shale, the turpentine liquid includes at leastone compound selected from natural turpentine, synthetic turpentine,mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol,β-terpineol, γ-terpineol, terpene resins, α-terpene, β-terpene,γ-terpene, or mixtures thereof. In other embodiments, the turpentineliquid includes at least one compound selected from geraniol, 3-carene,dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide,terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid includes at least one compoundselected from anethole, camphene; p-cymene, anisaldeyde,3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene, alloocimene,alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor,citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid,cintronellal, menthone, and mixtures thereof. In certain embodiments,the turpentine liquid can include α-terpineol. In other embodiments, theturpentine liquid can include at least about 40% by volume α-terpineoland between about 10 and 40% by volume β-terpineol. In certainembodiments, between 0.5 and 4 equivalents of the turpentine liquid isused to contact the oil shale and recover hydrocarbon-containing organicmatter. In certain embodiments, between 0.5 and 2.0 equivalents of theturpentine liquid is used to contact the oil shale and recoverhydrocarbons.

In another aspect, a method for recovering hydrocarbon-containingorganic matter from a coal rich sub-surface formation is provided. Themethod includes obtaining a coal, such as for example, by mining thesub-surface formation to produce coal, wherein the coal includes arecoverable hydrocarbon-containing organic matter and inorganic orinsoluble material. The coal is ground to produce crushed coal andfiltered to provide a sample of uniform or desired size. The crushedcoal is fed to a contacting vessel, wherein the contacting vesselincludes at least one inlet for supplying a hydrocarbon-extractingliquid consisting essentially of a turpentine liquid for recovery ofhydrocarbons from crushed coal, and contacted with thehydrocarbon-extracting liquid such that an extraction mixture is formedand a residual material is formed, wherein the extraction mixtureincludes at least a portion of the hydrocarbon-containing organic matterin the hydrocarbon-extracting liquid. The residual mixture includes atleast a portion of non-soluble material from the coal. The residualmatter is separated from the extraction mixture. Hydrocarbon containingorganic matter is separated from the hydrocarbon-containing liquid toproduce a hydrocarbon product stream that includes at least a portion ofthe hydrocarbon containing organic matter from the coal and ahydrocarbon-extracting liquid stream. In certain embodiments, the methodfurther includes recycling the hydrocarbon-extracting liquid stream tothe contacting vessel. In yet other embodiments, the liquid coal productstream is supplied to a liquid coal refinery. In certain embodiments,the coal sample includes a low grade coal having a mean particle size ofless than about 0.4 mm. In certain embodiments, the coal sample includesa high grade coal having a mean particle size of less than about 1 mm.

In yet other embodiments of the method for recoveringhydrocarbon-containing organic matter from coal, the turpentine liquidincludes at least one compound selected from natural turpentine,synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, or mixtures thereof. In other embodiments, theturpentine liquid includes at least one compound selected from geraniol,3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinanehydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol,p-menthan-8-ol, α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid includes at least one compoundselected from anethole, camphene; p-cymene, anisaldeyde,3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene, alloocimene,alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor,citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid,cintronellal, menthone, and mixtures thereof. In certain embodiments,the turpentine liquid includes at least 60 about by volume α-terpineol.In certain embodiments, the turpentine liquid includes at least about45% by volume α-terpineol and at least about 15% by volume β-terpineol.In certain other embodiments, the turpentine liquid includes at leastabout 60% by volume α-terpineol and up to about 30% by volumeβ-terpineol. In certain embodiments, between about 0.5 and 4 equivalentsof the turpentine liquid is used to contact the coal and recoverhydrocarbon-containing organic matter. In certain embodiments, between0.5 and 2.0 equivalents of the turpentine liquid is used to contact theoil shale and recover hydrocarbon-containing organic matter.

In another aspect, a method for increasing recovery ofhydrocarbon-containing organic matter from a production well isprovided, wherein the production well is coupled to ahydrocarbon-containing sub-surface formation that includeshydrocarbon-containing material. The method includes the steps ofextracting the hydrocarbon-containing organic matter by a process thatincludes the steps of providing an injection well that is in fluidcommunication with the sub-surface formation. A substantiallysurfactant-free first liquid is provided that includes a non-aqueoushydrocarbon-extracting liquid consisting essentially of a turpentineliquid that includes terpineol. The hydrocarbon-extracting liquid isinjected through the injection well and into the formation, wherein thehydrocarbon-extracting liquid and the hydrocarbon-containing organicmatter from the hydrocarbon containing sub-surface formation form anextraction mixture that includes at least a portion of the extractionmixture hydrocarbon-containing organic matter in at least a portion ofthe turpentine liquid. The extraction mixture is recovered from theformation through the production well, and the extraction mixture toproduce a hydrocarbon product stream and a turpentine liquid stream.

In another aspect, a system for recovering hydrocarbon-containingorganic material from tar sands is provided. The tar sands recoverysystem includes a tank for supplying a turpentine liquid and acontacting vessel, wherein the contacting vessel includes at least oneinlet for introducing the turpentine liquid and at least one outlet forrecovering an extraction mixture from the contacting vessel. The systemalso includes a first conveyor for supplying tar sands to the contactingvessel. A holding tank that includes a line connecting the holding tankto the contacting vessel is provided, wherein the line connecting thecontacting vessel and the holding tank includes a filter to prevent thepassage of solids to the holding tank. The system also includes a secondconveyor for the recovery and transport of the solids.

In one embodiment, the contacting vessel is a rotary inclined filterthat includes a series of fins or trays for separating and orcontrolling the tar sands. In another embodiment, the fins or trays areprovided to increase or control the contact time between the tar sandsand the turpentine liquid. In certain embodiments, the turpentine liquidcan include α-terpineol. In other embodiments, the turpentine liquid caninclude between about 30% and about 70% by volume α-terpineol andbetween about 25% and about 55% by volume β-terpineol.

In another aspect, a system for recovering hydrocarbon-containingorganic matter from oil shale is provided. The system includes a tankfor supplying a turpentine liquid and a grinder for comminuting the oilshale to a reduced particle size. A contacting vessel is provided thatincludes at least one inlet for introducing the turpentine liquid, atleast one inlet for receiving crushed oil shale, at least one outlet forrecovering solids from the contacting vessel and at least one outlet forrecovering an extraction mixture from the contacting vessel. A firstconveyor is provided for supplying crushed oil shale to a contactingvessel. The system further includes a holding tank, wherein the holdingtank includes a line connecting the holding tank to the contactingvessel, wherein the line includes a filter to prevent the passage ofsolids to the holding tank; a second conveyor for recovering solids. Incertain embodiments, the system further includes a line for supplying areaction mixture including recovered hydrocarbons and the turpentineliquid to a refinery for further separation and/or processing. Incertain embodiments, the turpentine liquid can include α-terpineol. Incertain embodiments, the turpentine liquid can include between about 60%and about 95% by volume α-terpineol and up to about 30% by volumeβ-terpineol. In other embodiments, the turpentine liquid can includebetween about 70% and about 90% by volume α-terpineol and between about5% and about 25% by volume β-terpineol.

In another aspect, a system for recovering hydrocarbon-containingorganic matter from coal is provided. The system includes a tank forsupplying a turpentine liquid and a grinder for comminuting coal toproduced particulate matter of a reduced size. Optionally, the systemcan include a filter to restrict the introduction of large particles. Acontacting vessel is provided that includes at least one inlet forintroducing the turpentine liquid and at least one outlet for recoveringsolids and liquids from the contacting vessel. The contacting vesselincludes also stirring means for thoroughly mixing the turpentine liquidand the comminuted coal. A separator is provided for separating thesolids and liquids, wherein the separator includes an inlet, an outletand a line connecting the inlet of the separator to the outlet of thecontacting vessel. The system also includes a holding tank, wherein theholding tank includes a line that connects the holding tank to theseparator, wherein the line can include a filter to prevent the passageof solids to the holding tank.

In certain embodiments, the system further includes a filter forselectively preventing particles having a mean diameter greater thanabout 1 mm from being introduced to the contacting vessel. In certainother embodiments, the system further includes a line for supplying aliquid coal product to a refinery for further processing. In certainembodiments, the system further includes a first conveyor for supplyingcrushed coal to the contacting vessel. In other embodiments, the systemfurther includes a second conveyor for removing solids from theseparator. In certain embodiments, the turpentine liquid can includeα-terpineol. In embodiments directed to the recovery of hydrocarbonsfrom high grade coal, the turpentine liquid can include between about45% and about 80% by volume α-terpineol and between about 15% and about45% by volume β-terpineol. In embodiments directed to the recovery ofhydrocarbons from low grade coal, the turpentine liquid can includebetween about 60% and about 95% by volume α-terpineol and between about0% and about 30% by volume β-terpineol.

In certain embodiments, the hydrocarbon-extracting liquid can beseparated from hydrocarbon-containing organic matter at, adjacent to, orin close proximity to the site of extraction of thehydrocarbon-containing material, i.e. coal, oil shale, tar sands, crudeoil, heavy crude oil, natural gas and petroleum gas, crude bitumen,kerogen, natural asphalt and/or asphaltene.

In further embodiments, the hydrocarbon-extracting liquid can bepartially separated from hydrocarbon-containing organic matter at,adjacent to, or in close proximity to the site of extraction. In suchembodiments, a portion of the hydrocarbon-extracting liquid is allowedto remain in the hydrocarbon-containing organic matter, thereby reducingviscosity and preventing corrosion during storage and transport.

In other embodiments, separation of the hydrocarbon-extracting liquidfrom hydrocarbon-containing organic matter occurs at a downstreamfacility which may be distant from the site of extraction, e.g. at arefinery.

In another aspect, partial or full separation of hydrocarbon-extractingliquids can apply to other methods of hydrocarbon recovery to obtain theadvantages provided by the present invention.

In another aspect, a method for optimizing a turpentine liquid forextraction of hydrocarbon-containing organic matter from hydrocarboncontaining matter is provided. Generally, the method includes providinga sample of the hydrocarbon-containing material and analyzing thehydrocarbon material to determine the type of hydrocarbon beingextracted. A formulation for extraction of hydrocarbon-containingorganic matter from the hydrocarbon material is provided, wherein theformulation is a function of the type of formation, general operatingconditions, and the size of the particulate hydrocarbon material.Generally, the formulation includes at least about 40% by volumeα-terpineol and at least about 10% by volume β-terpineol. The amount ofα-terpineol and β-terpineol in the formulation is then adjusted basedupon the parameters noted above. In general, while the above notedmethod provides a good starting point for determining the desiredformulation for extraction of various hydrocarbon containing materials,for other hydrocarbon-containing materials and under specified operatingconditions, either a series of statistically designed experiments or aseries of experiments according to an optimization method can beperformed to determine the optimum composition of the liquid turpentine.

As shown in Table 1, the specific formulation for extraction,liquefaction and/or solubilization of hydrocarbon-containing organicmatter from tar sands varies based upon the particle size. In certainembodiments, the method for preparing a turpentine liquid for extractinghydrocarbon-containing organic matter from tar sands includes adjustingthe amount of α-terpineol and β-terpineol in the formulation as afunction of the size of the hydrocarbon rich solid particulate beingextracted. In other embodiments, if the hydrocarbon-containing organicparticulate matter includes low grade coal or an oil shale, the amountα-terpineol in the turpentine liquid is increased and the amount ofβ-terpineol in the turpentine liquid is decreased. In other embodiments,if the hydrocarbon-containing organic particulate matter includes tarsands, the amount α-terpineol in the turpentine liquid is decreased andthe amount of β-terpineol in the turpentine liquid is increased. Inother embodiments, if the hydrocarbon-containing organic particulatematter includes tar sands and the mean diameter of the particulatematter is less than about 4.76 mm, then the amount α-terpineol in theturpentine liquid is decreased and the amount of β-terpineol in theturpentine liquid is increased. In other embodiments, if thehydrocarbon-containing organic particulate matter includes tar sands andthe mean diameter of the particulate matter is greater than about 25 mm(1 mesh), then the amount α-terpineol in the turpentine liquid isdecreased and the amount of β-terpineol in the turpentine liquid isincreased.

TABLE 1 Formulations for Extraction of Tar Sands based upon ParticleSize Particle Size (mm diameter) α-terpineol β-terpineol α-/β-terpeneother  <5 mm 30-50% vol 35-55% vol 10% vol 5% vol 5 mm-25 mm 40-60% vol30-50% vol 10% vol 5% vol >25 mm 50-70% vol 25-45% vol 10% vol 5% vol

Similar to what is shown above with respect to the extraction of tarsands, as shown in Tables 2 and 3, the formulation for extraction,liquefaction and/or solubilization of coal depends on particle size,quality of the coal being extracted, and general operating conditions.In one embodiment of the method for preparing a turpentine liquid forextracting hydrocarbon-containing organic matter, if thehydrocarbon-containing matter includes anthracite, bituminous coal, orother high grade coal and the mean diameter of the particulate matter isless than about 0.1 mm, then the amount of α-terpineol in the turpentineliquid is decreased and the amount of β-terpineol in the turpentineliquid is increased. In other embodiments, if the hydrocarbon richparticulate matter includes anthracite, bituminous coal, or other highgrade coal and the mean diameter of the particulate matter is greaterthan about 1 mm, then the amount of α-terpineol in the turpentine liquidis decreased and the amount of β-terpineol in the turpentine liquid isincreased. In another embodiment, if the hydrocarbon rich particulatematter includes low grade coal and the mean diameter of the particulatematter is less than about 0.07 mm, then the amount of α-terpineol in theturpentine liquid is decreased and the amount of β-terpineol in theturpentine liquid is increased. In another embodiment, if thehydrocarbon rich particulate matter includes low grade coal and the meandiameter of the particulate matter is greater than about 0.4 mm, thenthe amount of α-terpineol in the turpentine liquid is decreased and theamount of β-terpineol in the turpentine liquid is increased.

TABLE 2 Formulations for Extraction of High Grade Coal based uponParticle Size Particle Size (mm diameter) α-terpineol β-terpineolα-/β-terpene other <0.15 mm 45-65% vol 35-45% vol 10% vol 0% vol 0.8mm-0.15 mm 50-70% vol 20-40% vol 10% vol 0% vol  >0.8 mm 60-80% vol15-35% vol 10% vol 0% vol

TABLE 3 Formulations for Extraction of Low Grade Coal based uponParticle Size Particle Size (mm diameter) α-terpineol β-terpineolα-/β-terpene other <0.07 mm 60-80% vol 10-30% vol  5% vol 0% vol 0.07mm-0.4 mm 70-90% vol 5-25% vol 5% vol 0% vol  >0.4 mm 75-95% vol 0-20%vol 5% vol 0% vol

Similar to what is shown above with respect to the extraction of tarsands and coal, as shown in Table 4, the formulation for extraction,liquefaction and/or solubilization of oil shale depends on particlesize. In one embodiment of the method for preparing a composition forextracting hydrocarbon-containing organic matter, if the hydrocarbonrich particulate matter includes an oil shale and the mean diameter ofthe particulate matter is less than about 0.074 mm, then the amount ofα-terpineol in the turpentine liquid is decreased and the amount ofβ-terpineol in the turpentine liquid is increased. In anotherembodiment, if the hydrocarbon rich particulate matter includes oilshale and the mean diameter of the particulate matter is greater thanabout 0.42 mm, then the amount of α-terpineol in the turpentine liquidis decreased and the amount of β-terpineol in the turpentine liquid isincreased.

TABLE 4 Formulations for Extraction of Oil Shale based upon ParticleSize Particle Size (mm diameter) α-terpineol β-terpineol α-/β-terpeneother <0.07 mm 60-80% vol 10-30% vol  5% vol 0% vol 0.07 mm-0.4 mm70-90% vol 5-25% vol 5% vol 0% vol  >0.4 mm 75-95% vol 0-20% vol 5% vol0% vol

The formulation for the extraction of crude oil similarly depends on thetype of crude oil being extracted, liquefied, and/or solubilized. Asshown in Table 5, the formulation for the extraction, liquefactionand/or solubilization of crude oil is a function of both pore size andthe quality of the density of the crude oil being extracted. The methodincludes providing a turpentine liquid formulation that includes atleast about 50% by volume α-terpineol and at least about 20% by volumeβ-terpineol; adjusting the amount of α-terpineol and β-terpineol in theturpentine liquid formulation based upon the density of the liquidhydrocarbon being extracted. In one embodiment, if the API gravity ofthe liquid hydrocarbon being extracted is greater than about 22°, thenthe amount of α-terpineol in the turpentine liquid is decreased and theamount of β-terpineol in the turpentine liquid is increased. In anotherembodiment, if the API gravity of the liquid hydrocarbon being extractedis less than about 22, then the amount of α-terpineol in the turpentineliquid is increased and the amount of β-terpineol in the turpentineliquid is decreased. As used herein, light oils have an API of at leastabout 31°, medium crude oils have an API of between about 22° and about31°, heavy oil has an API of between about 10° and about 22°, and extraheavy oil has an API of less than about 10°.

TABLE 5 Formulations for Extraction of Crude Oil based upon API DensityCrude Type α-terpineol β-terpineol α-/β-terpene other Light/medium40-70% vol 30-40% vol 10% vol 10% vol crude (API greater than 22°)Heavy/Extra 50-70% vol 20-35% vol 10% vol  5% vol Heavy (API less than22°)

In another aspect, a method for preparing a turpentine liquid forenhancing recovery of liquid hydrocarbon-containing organic matter froma sub-surface formation is provided. The method includes providing aformulation comprising at least about 50% by volume α-terpineol and atleast about 20% by volume β-terpineol, and adjusting the amount ofα-terpineol and β-terpineol in the formulation based upon the geologicalfeatures of the sub-surface formation.

In another aspect, a composition for cleaning and/or recoveringhydrocarbons from a liquid hydrocarbon-containing vessel is provided,wherein the composition includes at least one compound selected fromnatural turpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In otherembodiments, the composition for cleaning and/or recovering hydrocarbonsincludes at least one compound selected from geraniol, 3-carene,dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide,terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In yet otherembodiments, the composition for cleaning and/or recovering hydrocarbonsincludes at least one compound selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof. In one embodiment, the compositionincludes at least one compound from the following: α-pinene, β-pinene,α-terpineol, and β-terpineol. In another embodiment, the compositionincludes at least about 25% by volume α-terpineol or β-terpineol.

In another aspect, a method for cleaning and/or recovering hydrocarbonsfrom a liquid hydrocarbon-containing vessel is provided. The methodincludes contacting the interior of vessel with a hydrocarbon cleaningcomposition that includes at least one compound selected from α-pinene,β-pinene, α-terpineol, and β-terpineol to create a mixture, wherein themixture includes the liquid hydrocarbon residue and the hydrocarboncleaning composition. The mixture is recovered and removed from thevessel. In certain embodiments, the cleaning composition includes atleast about 25% by volume of α-terpineol or β-terpineol. In certainother embodiments, the cleaning composition includes at least about 25%by volume of α-terpineol and at least about 25% by volume β-terpineol.

In one embodiment, the present invention provides a method of extractinghydrocarbon-containing organic matter from a hydrocarbon-containingmaterial, comprising extracting the hydrocarbon-containing organicmatter by a process comprising, consisting essentially of, or consistingof providing a substantially surfactant-free first liquid comprising anon-aqueous hydrocarbon-extracting liquid consisting essentially of aturpentine liquid, contacting the hydrocarbon-containing material withthe non-aqueous hydrocarbon extracting liquid such that an extractionmixture is formed, the extraction mixture comprising at least a portionof the hydrocarbon-containing organic matter extracted into thenon-aqueous hydrocarbon extracting liquid, and separating the extractionmixture from any residual material containing non-soluble material fromthe hydrocarbon-containing material that is not soluble in thenon-aqueous hydrocarbon extracting liquid.

In a further embodiment, the hydrocarbon-containing organic mattercontacts the hydrocarbon-extracting liquid in situ in an undergroundformation containing hydrocarbon-containing organic matter, and meansare provided for extracting hydrocarbon-containing organic matter froman underground formation.

In a further embodiment, the extraction mixture can be separated into afirst portion and a second portion, the first portion of the extractionmixture comprising a hydrocarbon product comprising at least a portionof the hydrocarbon-containing organic matter, the second portion of theextraction mixture comprising at least a portion of thehydrocarbon-extracting liquid.

In one embodiment, the amount of organic matter extracted from thehydrocarbon-containing material is at least about 50%. In anotherembodiment, at least about 70% of organic matter is extracted from thehydrocarbon-containing material. In a further embodiment from about75-100% of organic matter is extracted from the hydrocarbon-containingmaterial.

In another embodiment, for example when the material is super heavycrude oil e.g. Venezuelan extra heavy crude, the methods of the presentinvention are operable to extract at least about 30-35% of the amount oforganic matter from the hydrocarbon-containing material.

In a further embodiment, at least about 80% of hydrocarbons present in ahydrocarbon-containing material and extractable in the non-aqueoushydrocarbon extracting liquid can be extracted into the non-aqueoushydrocarbon extracting liquid within about 5 minutes of contacting. Inother embodiments, at least about 80% of hydrocarbons present in ahydrocarbon-containing material and extractable in the non-aqueoushydrocarbon extracting liquid can be extracted into the non-aqueoushydrocarbon extracting liquid within about 3 minutes of contacting.

In one embodiment, the hydrocarbon-containing material is contacted withhydrocarbon-extracting liquid in a ratio of at least 2:1 of turpentineliquid to hydrocarbon-containing material.

In certain embodiments with extraction, e.g., from coal, thehydrocarbons being extracted are predominantly from the volatilesportion of the coal, as opposed to fixed carbon in the coal.

In one embodiment, the hydrocarbon-containing material can be a naturalhydrocarbon-containing material from a naturally occurring geologicalformation. Some examples of natural hydrocarbon-containing materials arecoal, crude oil, tar, tar sands, oil shale, oil sands, natural gas,petroleum gas, crude bitumen, natural kerogen, natural asphalt, andnatural asphaltene.

In one embodiment of the method, the hydrocarbon-containing organicmatter is extracted into the hydrocarbon-extracting liquid in an amountthat corresponds to an amount of from about 1% to about 100% of thehydrocarbon-containing organic matter originally contained within thenatural hydrocarbon-containing material. In certain embodiments, atleast about 40 or 50%, in one embodiment at least about 60%, in anotherembodiment at least about 70%, in yet another embodiment at least about80%, and in another embodiment at least about 90% of thehydrocarbon-containing organic matter originally contained within thenatural hydrocarbon-containing material can be extracted into thehydrocarbon extracting liquid. Extraction of some or all of thehydrocarbon-containing organic matter from the naturalhydrocarbon-containing material into the hydrocarbon-extracting liquidcan take place from about 3 seconds to 180 minutes of contacting,between from about 97 seconds and 30 minutes, or between from about 15and 30 minutes, in one embodiment within less than about 10 minutes, inanother embodiment within less than about 5 minutes, in anotherembodiment within from 3 seconds to about 3 minutes at a contactingtemperature in a range of from about 10 to 400° C., in one embodimentless than 100° C., in another embodiment in a range of from about 20-30°C. at a weight ratio of hydrocarbon-extracting liquid to the naturalhydrocarbon-containing material of from about 10% to about 600%. Inanother embodiment the weight ratio of hydrocarbon-extracting liquid tothe natural hydrocarbon-containing material is from about 1:1 to 2:1.

In one embodiment, hydrocarbon-containing organic matter from coal isextracted into the hydrocarbon-extracting liquid in an amount thatcorresponds to an amount of from about 60 to 100% of thehydrocarbon-containing organic matter originally contained within thecoal sample and/or total carbon of at least from about 30% to 90% ofhydrocarbon-containing organic matter originally contained within thecoal sample within about 3 seconds to 3 minutes of contacting at acontacting temperature in a range of from about 80 to 100° C. at aweight ratio of hydrocarbon-extracting liquid to the coal of from about1:1 to 2:1.

In another embodiment, hydrocarbon-containing organic matter from tarsands is extracted into the hydrocarbon-extracting liquid in an amountthat corresponds to an amount of from about 85 to 100% of thehydrocarbon-containing organic matter originally contained within thetar sands sample within about 3 seconds to 3 minutes of contacting at acontacting temperature in a range of from about 30 to 60° C. at a weightratio of hydrocarbon-extracting liquid to the tar sands of from about1:1 to 2:1.

In another embodiment, hydrocarbon-containing organic matter from oilshale is extracted into the hydrocarbon-extracting liquid in an amountthat corresponds to an amount of from about 50 to 100% ofhydrocarbon-containing organic matter originally contained within theoil shale sample within about 3 seconds to 3 minutes of contacting at acontacting temperature in a range of from about 100 to 130° C. at aweight ratio of hydrocarbon-extracting liquid to the oil shale of fromabout 1:1 to 2:1.

In another embodiment, crude oil in an underground formation iscontacted with hydrocarbon-extracting liquid in situ in the undergroundformation. During contacting, hydrocarbon-containing organic matter fromthe crude oil extracted into the hydrocarbon-extracting liquid in anamount that corresponds to an amount of from about 80 to 100% ofhydrocarbon-containing organic matter originally contained within thecrude oil sample within about 3 seconds to 3 minutes of contacting at aratio of from about 1:1 to 1:2 of the hydrocarbon-extracting liquid tototal pore volume of the underground formation.

In another embodiment, hydrocarbon-containing organic matter fromnatural gas is extracted into the hydrocarbon-extracting liquid in anamount that corresponds to an amount of from about 50 to 100% ofhydrocarbon-containing organic matter originally contained within thenatural gas sample within from about 3 seconds to 60 minutes ofcontacting at a contacting temperature in a range of from about 10 to300° C. at a weight ratio of hydrocarbon-extracting liquid to saidhydrocarbon-containing material of from about 0.1 to 600%.

In another embodiment, the present invention provides a method formodifying sulfur compounds in a sulfur-containing hydrocarbon-containingmaterial from a natural geological formation by contacting or mixing thehydrocarbon-containing material with the hydrocarbon-extracting liquidsuch that the interaction of the turpentine liquid with sulfur in thehydrocarbon-containing material is operable to modify thehydrocarbon-containing material e.g. by inhibiting the corrosive andtoxic effects of a reactive sulfur species. Further, this embodiment ofthe invention can be applied to sweetening a gas. Sweetening isaccomplished through use of a sweetening module of a gas processingplant and may include trays, packing, or the like.

Sulfur-containing hydrocarbon-containing materials can include, but arenot limited to, natural gas, petroleum gas, crude oil, tar sands, oilshale, and coal. The sulfur may be present as elemental sulfur, hydrogensulfide, sulfides, disulfides, mercaptans, thiophenes, benzothiophenes,and the like.

In a further embodiment, sulfur-containing hydrocarbon containingmaterials in a gaseous form, such as natural gas or petroleum gas, canbe bubbled through the hydrocarbon-extracting liquid to sweeten the gas.

In one embodiment, the present invention provides a method of reducingthe corrosion of a corrodible surface. During transportation, drilling,downhole operations, exploration, hydrocarbon production, storage,handling, or production of hydrocarbon-containing material, for exampleby pipelines, tankers, casings, fishing tools, or drill bits, the metalsurfaces that contact sulfur-containing compounds in the hydrocarboncontaining materials may corrode. The present invention provides amethod for significantly reducing corrosion by the addition of acorrosion-reducing liquid to a hydrocarbon-containing material. Uniformand pitting corrosion can be inhibited by the methods of the presentinvention. When a hydrocarbon-containing material is mixed with thecorrosivity-reducing liquid thereby forming a mixture, the corrosionrate of the corrodible surfaces contacted with the mixture issubstantially reduced as compared to corrosion of these surfaces whencontacted with hydrocarbon-containing material in the absence of thecorrosion-reducing liquid. In one embodiment, the corrosivity-reducingliquid does not produce a stable sulfonated component. In anotherembodiment, sulfur does not accumulate in the turpentine extractionliquid.

In some embodiments, the mixture comprises at least from about 0.0001 to0.002% by volume of the corrosivity-reducing liquid. In anotherembodiment, the mixture comprises at least from about 0.0005% by volumeof the corrosivity-reducing liquid. In a further embodiment, the mixturecomprises at least from about 0.001% by volume of thecorrosivity-reducing liquid. In a further embodiment, the mixturecomprises at least from about 0.0015% by volume of thecorrosivity-reducing liquid. In a further embodiment, the mixturecomprises at least from about 0.001% to 0.002% by volume of thecorrosivity-reducing liquid. In another embodiment, the mixturecomprises at least from about 0.01% to 10% by volume of thecorrosivity-reducing liquid. In a further embodiment, the mixturecomprises at least from about 0.1% to 5% by volume of thecorrosivity-reducing liquid. In yet another embodiment, the mixturecomprises at least from about 0.5% to 2% by volume of thecorrosivity-reducing liquid. In a further embodiment, the mixturecomprises at least from about 1% by volume of the corrosivity-reducingliquid.

In a further embodiment, the rate of corrosion is reduced by at leastabout 2-fold as compared to corrosion of the surface when contacted witha hydrocarbon-containing material in an absence of thecorrosivity-reducing liquid.

In another embodiment the rate of corrosion is reduced by at least about3-fold. In a further embodiment, the rate of corrosion is reduced by atleast about 4-fold as compared to corrosion of the surface whencontacted with a hydrocarbon-containing material in an absence of thecorrosivity-reducing liquid.

In one embodiment, the corrosivity-reducing liquid includes α-terpineol,β-terpineol, β-pinene, and p-cymene. In another embodiment thecorrosivity-reducing liquid includes about 40% to about 60% α-terpineol,about 30% to about 40% β-terpineol, about 5% to about 20% β-pinene, andabout 0 to about 10% p-cymene. In a further embodiment, thecorrosivity-reducing liquid comprises a blend of turpentine liquids.

In certain embodiments, the hydrocarbon-containing material treated withcorrosivity-reducing liquid is crude oil, heavy crude oil, tar sands,oil sands, oil shale, natural gas, petroleum gas, or a combinationthereof.

In another embodiment, the present invention provides a method ofpreparing a hydrocarbon-containing gas by contacting ahydrocarbon-containing material with a substantially surfactant-freefirst liquid that includes a non-aqueous hydrocarbon-extracting liquid,wherein the non-aqueous hydrocarbon-extracting liquid includes aturpentine liquid, forming a mixture, wherein the mixture comprises atleast a portion of the hydrocarbon-containing organic matter extractedinto the hydrocarbon-extracting liquid, and heating the mixture to forma gas containing the hydrocarbon-extracting material and hydrocarbonsextracted from the hydrocarbon-containing material.

In certain embodiments, the hydrocarbon-containing material is crudeoil, heavy crude oil, tar sands, oil sands, oil shale, natural gas,petroleum gas, or a combination thereof.

The present invention provides a method for increasing recovery ofhydrocarbon-containing organic matter from a production well coupled toa hydrocarbon-containing sub-surface formation containinghydrocarbon-containing material. The method includes: providing aninjection well in fluid communication with the sub-surface formation,injecting a substantially surfactant-free first liquid comprising anon-aqueous hydrocarbon-extracting liquid consisting essentially of aturpentine liquid, e.g. terpineol, into the formation to form anextraction mixture comprising at least a portion of the extractionmixture hydrocarbon-containing organic matter in at least a portion ofthe turpentine liquid, recovering the extraction mixture from theformation through the production well, and separating the extractionmixture to produce a hydrocarbon product stream and a turpentine liquidstream. The hydrocarbon-extracting liquid can be recycled forreinjection.

The present invention provides a method for recoveringhydrocarbon-containing organic matter from tar sands. The methodinvolves obtaining tar sands comprising recoverablehydrocarbon-containing organic matter, providing a substantiallysurfactant-free first liquid comprising a hydrocarbon-extracting liquidcomprising a turpentine liquid comprising at least one of α-terpineol orβ-terpineol, supplying the tar sands sample to a contacting vessel,contacting the tar sands sample with the hydrocarbon-extracting liquidin a contacting vessel and agitating the tar sands sample with thehydrocarbon-extracting liquid such that an extraction mixture is formedand a residual material is formed. separating the extraction mixturefrom the residual material, separating the extraction mixture into ahydrocarbon product stream and a hydrocarbon-extracting liquid stream,and recycling at least a portion of the hydrocarbon-extracting liquidstream to the contacting step. The extraction mixture includes at leasta portion of the hydrocarbon-containing organic matter in thehydrocarbon-extracting liquid and the residual material includes atleast a portion of non-soluble material from the tar sands that is notsoluble in the hydrocarbon-extracting liquid and the hydrocarbon productstream includes at least a portion of the hydrocarbon-containing organicmatter from the tar sands.

The present invention provides a method for recoveringhydrocarbon-containing organic matter from comminutedhydrocarbon-containing oil shale. The method involves contacting thecomminuted hydrocarbon-containing oil shale with a substantiallysurfactant-free first liquid comprising a non-aqueoushydrocarbon-extracting liquid consisting essentially of a turpentineliquid selected from the group consisting of natural turpentine,synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof, filtering the comminutedhydrocarbon-containing oil shale, feeding the crushedhydrocarbon-containing oil shale to a contacting vessel, contacting thecomminuted hydrocarbon-containing oil shale with thehydrocarbon-extracting liquid such that an extraction mixture is formedand a residual material is formed, separating the extraction mixturefrom the residual material, separating the hydrocarbon-containingorganic matter from the hydrocarbon-extracting liquid in the extractionmixture to produce a hydrocarbon product stream and ahydrocarbon-extracting liquid stream, the hydrocarbon product streamcomprising at least a portion of the hydrocarbon-containing organicmatter from the comminuted hydrocarbon containing oil shale, andrecycling at least a portion of the hydrocarbon-extracting liquid streamto the contacting step. The extraction mixture comprising at least aportion of the hydrocarbon-containing organic matter in thehydrocarbon-extracting liquid, the residual material comprising at leasta portion of non-soluble material from the oil shale that is not solublein the hydrocarbon-extracting liquid

The present invention provides a method for recoveringhydrocarbon-containing organic matter from hydrocarbon-containing coalrich sub-surface formation. The method involves obtaining and grindingcoal comprising a recoverable hydrocarbon-containing organic matter toproduce crushed coal, filtering the crushed coal, feeding the crushedcoal to a contacting vessel, said contacting vessel which has at leastone inlet for supplying a hydrocarbon-extracting liquid to thecontacting vessel, contacting the crushed coal with a substantiallysurfactant-free non-aqueous hydrocarbon-extracting liquid consistingessentially of a turpentine liquid selected from the group consisting ofnatural turpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof such that an extraction mixture is formedand a residual material is formed, the extraction mixture comprising atleast a portion of the hydrocarbon-containing organic matter in thehydrocarbon-extracting liquid, the residual material comprising at leasta portion of non-soluble material from the coal that is not soluble inthe hydrocarbon-extracting liquid, separating the residual material fromthe extraction mixture, separating the hydrocarbon-containing organicmatter from the hydrocarbon-extracting liquid to produce a hydrocarbonproduct stream and a hydrocarbon-extracting liquid stream, thehydrocarbon product stream comprising at least a portion of thehydrocarbon-containing organic matter from the coal, and recycling atleast a portion of the hydrocarbon-extracting liquid stream to thecontacting step, wherein said first liquid contains no water oressentially no water.

EXAMPLES Example 1

In this example, coal from the Pittsburgh seam in Washington County,Pennsylvania was liquefied with reagent α-terpineol. The coal sample wasobtained from the Coal Bank at Pennsylvania State University, whichprovided the following proximate analyses for it; 2.00 wt. % ofas-received moisture, 9.25 wt. % of dry ash, 38.63 wt. % of dry volatilematter, and 50.12 wt. % of dry fixed carbon. The particle size of coalsample was about 60 mesh. About 60 grams of α-terpineol was gently addedto about 30 grams of the coal sample placed in an extraction vessel,thus giving rise to the reagent-to-sample ratio of 2 to 1. The capped,but not tightly sealed, extraction vessel containing the resultantmixture of α-terpineol and coal was maintained at the constanttemperature of about 96° C. and continually agitated. Without boilingthe α-terpineol, the pressure in the extraction vessel remained at theambient pressure of slightly less than about 1.01×10⁵ Pascals (1 atm).After about 30 minutes, the mixture was filtered and the coal particlesretained on the filter were washed with ethanol and dried to a constantweight. On the basis of weight loss, the conversion, i.e., the extent ofliquefaction, of the coal sample was determined to be about 68 wt. %.

Example 2

This Example is identical to Example 1 in all aspects except two. Aftermaintaining the temperature at about 96° C., for about 30 minutes, asdone in Example 1, the extraction vessel containing the coal sample andα-terpineol was maintained at a temperature at about 135° C. for anadditional period of about 30 minutes. The pressure in the extractionvessel remained at the ambient pressure of slightly less than about1.01×10⁵ Pascals (1 atm). The conversion, i.e., the degree ofliquefaction, of the coal sample was determined to be about 70 wt. %.

Example 3

The coal sample used was from the same source with the same proximateanalyses as those used in the preceding two examples. About 31 grams ofα-terpineol were added to about 31 grams of the coal sample in anextraction vessel. The mixture was maintained at about 96° C. and anambient pressure of slightly less than about 1.01×10⁵ Pascals (1 atm)for about 30 minutes. The conversion, i.e., the degree of liquefaction,of the coal sample attained was determined to be about 71 wt. % byweighing the sample after filtering, washing, and drying as done in thepreceding two examples.

Example 4

This Example is identical to Example 3, except that about 30 wt. % ofα-terpineol was replaced with hexane, providing a reagent that includes70 wt. % α-terpineol and 30 wt. % hexane. This reduced the conversion,i.e., the degree of liquefaction to about 1.3 wt. %.

Example 5

The source and proximate analyses of coal sample and experimentalconditions in terms of temperature, pressure and reagent-to-sample ratiofor this example were the same as those of Example 3. The duration ofthe extraction, however, was reduced from about 30 minutes to about 20minutes. Additionally, about 30 wt. % of the α-terpineol was replacedwith 1-butanol, providing a reagent that includes 70 wt. % α-terpineoland 30 wt. % 1-butanol. The amount of coal liquefied was only about 0.30gram, corresponding to conversion of about 1.0 wt. %.

Example 6

This Example is the same as Example 3 in terms of the source andproximate analyses of coal sample and temperature, pressure and durationof the extraction. The amount of the coal sample used was, however,about 25 grams and the reagent comprised about 24 grams (80 wt. %) ofα-terpineol and about 6 grams (20 wt. %) of xylenes, providing a reagentthat includes 70 wt. % α-terpineol and 30 wt. % xylenes. The coalliquefied was about 10.0 grams, corresponding to conversion of about 40wt. %.

Example 7

In this example, coal from the Wyodak seam in Campbell County,

Wyoming was liquefied with reagent α-terpineol. The coal sample wasobtained from the Coal Bank at Pennsylvania State University, whichprovided the following proximate analyses for it; 26.30 wt. % ofas-received moisture, 7.57 wt. % of dry ash, 44.86 wt. % of dry volatilematter, and 47.57 wt. % of dry fixed carbon. The coal sample's particlesize was about 20 mesh. About 60 grams of α-terpineol was gently addedto about 30 grams of the coal sample placed in an extraction vessel, areagent-to-sample ratio of about 2 to 1. The capped, but not tightlysealed, extraction vessel containing the resultant mixture ofα-terpineol and coal was maintained at a constant temperature of about96° C. and continually agitated. Without boiling of the α-terpineol, thepressure in the extraction vessel remained at the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). After about 30minutes, the mixture in the extraction vessel was filtered and the coalparticles retained on the filter were washed with ethanol and dried to aconstant weight. On the basis of weight loss, the conversion, i.e., thedegree of liquefaction, of the coal sample was determined to be 75 wt.%.

Example 8

The experiment in this example was carried out under the conditionsidentical to those of the preceding example except one. About 15 gramsof α-terpineol were added, instead of about 60 grams, as done in thepreceding example, to about 30 grams of the coal sample, thus attainingthe reagent-to-coal ratio of 0.5 to 1. The conversion, i.e., the degreeof liquefaction, of the coal sample attained decreased from about 75 wt.%, attained in the preceding example, to about 69 wt. %.

Example 9

In this example, about 3 grams of oil shale from the Green-river regionof Colorado was solubilized with about 9 grams of α-terpineol, thusgiving rise to the reagent-to-sample ratio of 3 to 1, to extract kerogen(organic matter) and/or bitumen (organic matter) from it. The organiccarbon content, including both volatile and fixed carbon, was determinedto be about 22.66 wt. % by a certified analysis company. Two experimentswith the oil-shale samples, having the particle size of 60 mesh, werecarried out under the ambient temperature and pressure of about 25° C.and slightly less than about 1.01×10⁵ Pascals (1 atm), respectively. Theweight losses of the samples were determined by weighing afterfiltering, washing with ethanol, and drying. These losses were about 9wt. % after about 30 minutes and about 17 wt. % after about 45 minutes.From these weight losses, the conversion, i.e., the degree of extractionof organic matter, i.e., kerogen and/or bitumen, was estimated to beabout 40 wt. % for the former and was about 75 wt. % for the latter.

Example 10

This Example duplicated the preceding example with the exception that asingle experiment, lasting about 15 minutes, was carried out at thetemperature of about 96° C., instead of about 25° C. The weight loss ofthe oil shale sample was about 12 wt. %, corresponding to theconversion, i.e., the degree of extraction, of kerogen (organic matter)of about 53 wt. %

Example 11

In this example, bitumen (organic matter) in tar sands from Alberta,Canada, was solubilized and extracted with commercial grade syntheticturpentine. The tar-sands sample was obtained from Alberta ResearchCouncil, which provided the following proximate analyses for it; 84.4wt. % of dry solids, 11.6 wt. % of dry bitumen, and 4.0 wt. % ofas-received moisture. About 30 grams of synthetic turpentine were gentlyadded to about 15 grams of the tar-sands sample in a capped, but nottightly sealed, extraction vessel, utilizing a reagent-to-sample ratioof about 2 to 1 by weight. This extraction vessel, containing theresultant mixture of synthetic turpentine and tar sands, was maintainedat a constant temperature of about 96° C. and continually agitated.Without boiling of the synthetic turpentine, the pressure in theextraction vessel remained at the ambient pressure of slightly less thanabout 1.01×10⁵ Pascals (1 atm). After about 20 minutes, the mixture inthe extraction vessel was filtered and the solids (tar sands) retainedon the filter were washed with ethanol and dried to a constant weight.On the basis of weight loss, the conversion, i.e., the degree ofextraction, of bitumen from the tar-sands sample was determined to beabout 100 wt. %.

Example 12

In this example, about 60 grams of the tar-sands sample from the samesource with the same proximate analyses as those of the precedingexample were extracted by about 60 grams of α-terpineol, instead ofcommercial-grade synthetic turpentine, which includes α-terpineol. Theresultant reagent-to-sample ratio was 1 to 1 instead of 2 to 1 as in thepreceding example. The experiment lasted about 30 minutes at thetemperature of about 96° C. under the ambient pressure of slightly lessthan about 1.01×10⁵ Pascals (1 atm). The conversion, i.e., the extent ofextraction, of bitumen (organic matter) in the tar-sands sample wasdetermined to be about 100 wt. %.

Example 13

In this example, about 60 grams of the tar-sands sample from the samesource with the same proximate analyses as those of the preceding twoexamples were extracted by about 60 grams of synthetic turpentine, whichis of the commercial grade. The resultant reagent-to-sample ratio,therefore, was about 1 to 1. The experiment was carried out for about 30minutes at the temperature of about 96° C. under the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). The conversion, i.e.,the degree of extraction, of bitumen (organic matter) in the tar-sandssample was determined to be about 70 wt. %.

Example 14

The experiment in this example duplicated that in Example 8 in allaspects except that the reagent-to-sample ratio was reduced from about 2to 1 to about 0.5 to 1: About 60 grams to the tar-sands sample wasextracted by about 30 grams of synthetic turpentine, which is of thecommercial grade. The conversion, i.e., the degree of extraction, ofbitumen (organic matter) decreased from about 100 wt. % attained inExample 9 to about 70 wt. %.

Example 15

The experiment in this example repeated that of the preceding examplewith α-terpineol instead of the commercial-grade synthetic turpentine.The conversion, i.e., the degree of extraction, of bitumen (organicmatter) in the tar-sands sample was about 70 wt. % as in the precedingexample.

Example 16

The experiment in this example was carried out under the ambientpressure of slightly less than about 1.01×10⁵ Pascals (1 atm) with thetar-sands sample from the same source with the same proximate analysesas those in the preceding examples with tar sands. About 60 grams ofcommercial-grade synthetic turpentine was added to about 60 grams of thetar-sands sample, thus giving rise to the reagent-to-sample ratio ofabout 1 to 1. The temperature of the sample and commercial-gradesynthetic turpentine was maintained at about 65° C. for about 30 minutesfollowed by cooling to about 15° C. within about 5 minutes.Subsequently, the tar-sands sample was filtered, washed, dried andweighed. On the basis of weight loss, the conversion, i.e., the degreeof extraction, of bitumen (organic matter) in the tar-sands sample wasdetermined to be about 70 wt. %.

Example 17

The experiment in this example repeated that of the preceding examplewith α-terpineol instead of commercial grade synthetic turpentine. Theconversion, i.e., the degree of extraction, of bitumen (organic matter)increased to about 90 wt. % from about 70 wt. % of the precedingexamples.

Example 18

In this example, a tar-sands sample, weighing about 30 grams, from thesame source with the same proximate analyses as those in Examples 11through 17, was extracted with a liquid that included about 20 grams (80wt. %) of α-terpineol and about 5 grams (20 wt. %) of toluene at thetemperature of about 96° C. under the ambient pressure of slightly lessthan about 1.01×10⁵ Pascals (1 atm). The duration of the experiment(reaction or extraction time) was about 30 minutes. The weigh loss ofthe sample was about 10.2 grams. From this weigh loss, the conversion,i.e., the degree of extraction, of bitumen (organic matter) wasestimated to be about 33 wt. %.

Example 19

Three tar-sands samples, all from the same source with the sameproximate analyses as those used in all preceding examples with tarsands were extracted by reagents comprising various amounts ofα-terpineol and ethanol at the temperature of about 15° C. under theambient pressure of slightly less than about 1.01×10⁵ Pascals (1 atm).The duration of each experiment (reaction or extraction time) was about15 minutes for each tar-sands sample. The first sample was extractedwith a mixture comprising about 0 gram (0 wt. %) of α-terpineol andabout 15 grams (100 wt. %) of ethanol, i.e., with pure ethanol. Thesecond sample was extracted with a mixture comprising about 7.5 grams(50 wt. %) of α-terpineol and about 7.5 grams (50 wt. %) of ethanol. Thethird sample was extracted with a mixture comprising about 12 grams (80wt. %) of α-terpineol and about 3 grams (20 wt. %) of ethanol. Theweight losses and the estimated conversions, i.e., the degrees ofextraction, of bitumen (organic matter) in the three samples were about0.2 gram (1.0 wt. %), 0.6 gram (3.0 wt. %) and 0.9 gram (4.5 wt. %), forthe first, second and third sample, respectively.

Example 20

Irregular-shaped pellets of commercial-grade asphalt whose average sizewas about 15 mm were solubilized and extracted with α-terpineol and atthe ambient temperature of about 22° C. under the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). The first sampleweighing about 20 grams was solubilized and extracted with about 40grams of α-terpineol, and the second sample also weighing about 20 gramswas solubilized and extracted with about 20 grams of α-terpineol. Thehydrocarbons in both samples were completely extracted after 30 minutes.These experiments were carried out to simulate the solubilization andextraction of heavy crude oil, which tends to be rich in asphalteneslike asphalt.

Example 21

In this example, bitumen (organic matter) in tar-sands from the samesource with the same proximate analyses as those used in all previousexamples with tar sands was solubilized and extracted with two varietiesof vegetable oils, soybean oil and corn oil. The vegetable oils arecompletely miscible with turpentine liquid. In the first experiment, atar-sands sample weighing about 15 grams was blended and agitatedcontinually with about 30 grams of soybean oil for about 20 minutes atthe temperature of about 96° C. under the ambient pressure of slightlyless than about 1.01×10⁵ Pascals (1 atm). The weight loss was about 0.5gram from which the conversion, i.e., the degree of extraction, ofbitumen in the sample was estimated to be about 3.3 wt. %. In the secondexperiment, a tar-sands sample weighing about 30 grams was blended andagitated continually with about 60 grams of corn oil for about 30minutes at the temperature of about 175° C. under the ambient pressureof slightly less than about 1.01×10⁵ Pascals (1 atm). The weight losswas about 4.8 grams from which the conversion, i.e., the degree ofextraction, of bitumen in the sample was estimated to be about 12 wt. %.

Example 22

Two tests were performed on Berea sandstone plug core samples todetermine the effect of reagent injection on oil recovery from core. Thefirst test was designed to determine the increment oil recovery due toα-terpineol injection after a field had already undergone waterfloodingto the limit. The selected core contained 9.01 mL of laboratory oilsimulating crude oil. The waterflooding with aqueous solution containing3.0% of potassium chloride produced 4.6 mL of oil. Five (5) pore volumesof α-terpineol injection produced additional 3.61 mL of oil, therebyleaving the core with less than 8.0% of oil remaining in the originalvolume. The second test was designed to represent the increased recoverythat could be expected from a virgin reservoir with α-terpineolinjection. The selected core contained 8.85 mL of laboratory oilsimulating crude oil. Oil production began after approximately 0.5 porevolumes of α-terpineol injection, and continued until 3.5 pore volumesof α-terpineol had been injected; however, the majority of the oil wasrecovered after only 2.5 pore volumes of α-terpineol injection. A totalof 7.94 mL of laboratory oil was recovered, thereby leaving the corewith less than 7.5% of oil remaining in the original volume.

In one experiment, various ratios of a turpentine liquid to tar sandssample were tested. The turpentine liquid for each of the experimentsprovided below had the same formulation, wherein the compositionincluded about 60% by volume α-terpineol, about 20% by volumeβ-terpineol, and about 20% by volume γ-terpineol. The tar sands were adifferent mix of ores from Alberta, Canada, having a bitumen content ofapproximately 12% by weight and a water content of between about 4-5% byweight. The experiments were all performed at various temperatures aslisted in Table 6.

As shown in Table 6 below, recovery of hydrocarbons from tar sandsacross all ratios provided below (i.e., ratios of turpentine liquid totar sands ranging from about 1:2 to about 2:1) resulted in good recoveryof hydrocarbons and little discernible difference. With respect to thetemperature at which the extraction is carried out, it is believed thatthe optimum temperature for the extraction, solubilization and/orliquefaction of hydrocarbons from tar sands is about 65° C. As shown inthe table, at about 130° C., the amount of hydrocarbons recovered fromthe tar sands is reduced. It is noted however, that for certain solidsfrom which it is particularly difficult to recover hydrocarbons,increasing the temperature of the extraction solvent can increase theamount of hydrocarbons that are recovered. Finally, it is shown thatexposure time had very little effect on the amount of materials thatwere extracted. This is likely because the shortest extraction time wasabout 20 minutes, which is believed to be more than adequate for theextraction of the hydrocarbons from tar sands.

TABLE 6 Weight of Ratio of Amount Percent Exposure Tar Sands Extractableextraction tar sands of HC HC Temp, Time, Weight, g HC weight, g solventto solvent extracted, g extracted ° C. minutes 15 2.0 30.0 1:2 3.2 16196 20 60 7.8 120.0 1:2 5.4 69 96 30 60 7.8 31.6 2:1 9.6 123 96 30 60 7.860.0 1:1 7.6 97 65 30 60 7.8 60.0 1:1 4.0 51 130 30 60 7.8 60.0 1:1 6.380 65 30

Additional experiments were conducted using alternative solvents, namelyethanol and corn oil, which was compared with the composition thatincluded about 60% by volume α-terpineol, about 20% by volumeβ-terpineol, and about 20% by volume γ-terpineol. As noted in Table 7provided below, the performance of ethanol and corn oil wereunexpectedly substantially lower than the composition that includedabout 60% by volume α-terpineol, about 20% by volume β-terpineol, andabout 20% by volume γ-terpineol. For example, whereas the terpineolcomposition achieved complete or nearly complete extraction ofextractable hydrocarbons, ethanol yielded only about 10% of therecoverable hydrocarbons and heated corn oil yielded only about 33% ofthe recoverable hydrocarbons.

TABLE 7 Extractable Weight of Ratio of Amount Percent Exposure Tar SandsHC extraction tar sands of HC HC Temp, Time, Chemical Weight, g weight,g solvent to solvent extracted, g extracted ° C. minutes Ethanol 15 2.015.0 1:1 o.2 10 15 15 Corn oil 30 3.9 60.0 2:1 1.3 33 175 30 60/20/20 607.8 60.0 1:1 7.6 97 65 30 terpineol 60/20/20 60 7.8 31.6 2:1 9.6 123 9630 terpineol

As shown in Table 8 below, the performance of various turpentine liquidformulations, including turpentine liquid formulations that include onlyα-terpineol and α-terpineol in combination with various known organicsolvents, are provided. The first three compositions presented in thetable include α-terpineol, β-terpineol, and γ-terpineol. For example,the first same includes about 60% by volume α-terpineol, about 30% byvolume β-terpineol, and about 10% by volume γ-terpineol. The resultsunexpectedly show that as the concentration of the α-terpineolincreases, performance of the turpentine liquid increases to the pointthat when the turpentine liquid includes approximately 70% α-terpineol,full extraction of the hydrocarbon material from the tar sands sample isachieved.

The second set of data is presented for extraction of hydrocarbonbearing tar sands with pure α-terpineol. As shown, extraction of greaterthan 100% is achieved, likely due to inconsistencies in the hydrocarboncontent of the samples. However, the results generally demonstrate theunexpected result that α-terpineol is capable of extractingsubstantially all of the recoverable hydrocarbon from a tar sandssample.

The data provided in Table 8 illustrates the effectiveness of mixedsystems of α-terpineol and known organic solvents. As shown,substantially complete recovery of recoverable hydrocarbons is achievedwith a composition that includes about a 1:1 ratio of α-terpineol toethanol. This is unexpected as pure ethanol only removed about 10% ofthe total recoverable hydrocarbons. Additionally, mixed systems thatinclude either a 1:1 or a 3:1 ratio of α-terpineol to toluene stillresulted in the recovery of about 77% and 92% of the total recoverablehydrocarbons. This was an unexpected result.

TABLE 8 Ratio of Amount Percent Exposure Chemical Tar Sands ExtractableWt. Of tar sands of HC HC Temp, Time, comp. wt., g HC wt., g solvent tosolvent extracted, g extracted ° C. minutes 60/30/10 60 2.0 60.0 1:1 7.191 96 30 terpineol 40/30/20 60 7.8 60.0 1:1 4.7 60 96 30 terpineol70/20/10 60 7.8 60.0 1:1 7.9 101 96 30 terpineol 100/0/0 60 7.8 60.0 1:110.0 128 96 30 terpineol 100/0/0 60 7.8 120.0 1:2 8.7 111 96 30terpineol 100/0/0 60 7.8 31.0 2:1 9.6 123 96 30 terpineol 50% α- 15 2.015.0 1:1 8.1 103 65 30 terpineol/ 50% ethanol 80% α- 15 2.0 15.0 1:1 1.262 15 15 terpineol/ 20% ethanol 75% α- 30 3.9 25.0  1:0.8 1.8 92 15 15terpineol/ 25% toluene 50% α- 30 3.9 26.0  1:0.9 3.0 77 96 30 terpineol/50% toluene 50% α- 30 3.9 26.0  1:0.9 2.4 61 96 30 terpineol/ 50%xylenes

Example 23

Approximately 30 g tar sands samples were sprayed with each of thefollowing liquids: d-limonene, a blend of turpentine liquids, and wateras a control. Temperature was maintained at about 18° C. The percent ofbitumen recovered was measured after a contact time of about 5, 10, 15,20, 25, and 30 seconds. The blend of turpentine liquids was a moreeffective extractor than d-limonene, whereas water was ineffective (seeFIG. 5).

Example 24

Approximately 15 g tar sands samples were sprayed with d-limonene or ablend of turpentine liquids and left in contact with the liquid for 97seconds. The ratio of liquid to tar sands ranged from approximately 1:1to approximately 6:1. From 54% recovery at 1:1 to 84% recovery at 6:1ratios, the blend of turpentine liquids extracted more bitumen than thelimonene across the range of mixing ratios (see FIG. 6).

Example 25

The effectiveness of a number of turpentine liquid species andcombinations for extracting hydrocarbon was measured relative to theability of each liquid to recover bitumen from a tar sands sample. Ineach test, an approximately 15 g tar sands sample was treated at about18° C. with one of the following turpentine liquids: α-terpineol,β-terpineol, β-pinene, α-pinene p-cymene, d-limonene, and a blend ofturpentine liquids. The percent of bitumen recovered was measured aftercontact times of about 5 (FIG. 7) and about 15 (FIG. 8) minutes. Thedata show that all of the liquids extracted a substantial amount of thebitumen from the tar sands. The blend of turpentine liquids was the mosteffective extractor across the range of liquid to material ratios,recovering nearly all of the bitumen content within about 5 minutes ofcontact (see FIG. 7).

Example 26

The amount of SAE 40 (a medium-weight crude oil) that could be extractedby a blend of turpentine liquids was compared against n-butanol,cyclohexanol, and 1-heptanol. At 35° C., it was found that the amount ofSAE 40 extracted into 100 ml of a blend of turpentine liquids consistingof about 50% α-terpineol, about 35% β-terpineol, about 10% β-pinene, andabout 5% p-cymene was approximately 8.14-, 6.67-, and 7.46-fold morethan the amount of SAE 40 that was extracted into 100 ml n-butanol, 100ml cyclohexanol, and 100 ml 1-heptanol, respectively. Each of thealkaline solutions contained 150 ml of 97% sodium metasilicate.

Example 27

Approximately 15 g and 30 g samples of paraffin wax, and approximately100 g samples of asphaltines were extracted into 100% α-terpineol and100% of a blend of turpentine liquids at about 60° C. for about 15minutes. Table 9 shows the percentage of hydrocarbon solids that wereextracted into the turpentine liquids.

Comparative Example

In a comparative example, the use of a liquid consisting of about ⅓terpenoids (limonene, pinene), about ⅓ heavy petroleum distillates, andabout ⅓ light petroleum distillates to liquefy paraffin waxes andasphaltenes was compared against α-terpineol and the multi-componentturpentine system using the same method as described in Example 27. Acomparison of the percentage of paraffin wax and asphaltines extractedis shown in Table 9.

TABLE 9 % extracted % extracted 15 g 30 g 100 g 100 g paraffin paraffinasphaltine asphaltine Solvent wax wax (1) (2) ⅓ β-Pinene, ⅓ heavy 60 6042 47 crude, ⅓ light crude Alpha terpineol 100 100 100 100 Blend ofturpentine liquids 93.3 90 100 100

Example 28

Table 10 shows the decrease in viscosity of oils of different weightsafter contact with turpentine liquids. Measurements were taken within 20seconds at a temperature of about 21° C. The largest percentage drop inviscosity is obtained by contacting heavier oils with a blend ofturpentine liquids.

TABLE 10 Type of Viscosity Reducing Liquid % viscosity Oil (weight %ratio to oil) Viscosity decrease SAE 40 None 718-750 N/A SAE 40α-terpineol (10%) 697-699  7% (mean) SAE 40 α-terpineol (15%) 569-62021% (mean) SAE 40 Blend of turpentine liquids (10%) 297 60% SAE 40 Blendof turpentine liquids (15%) 245 67% SAE 30 None 156 N/A SAE 30 Blend ofturpentine liquids (10%) 109 30% SAE 30 Blend of turpentine liquids(15%) 88 44% SAE 10 None 49 N/A SAE 10 Blend of turpentine liquids (10%)35 29%

Example 29

Corrosion Test. API X-65 carbon steel coupons (METAL SAMPLES COMPANY,Munford, Ala., USA) were exposed to ASTM substitute seawater with 500ppm Na₂S, pH adjusted to about 4.8 using acetic acid, under continuousflow for two weeks. A control sample contained only a baseline solutionof the seawater in the absence of corrosion inhibitor. Samples I, II,and III contained about 0.0005%, 0.001%, and 0.0015% by volume of ablend of turpentine liquids. The corrosion rates recorded directlycoincide with the amount of crevice attack observed on each test coupon.Sample III, consisting of about 0.0015% by volume of a blend ofturpentine liquids produced the lowest average corrosion rate (see Table11) and no pitting corrosion.

TABLE 11 Initial weight of Final weight of Average coupon (g) coupon (g)corrosion rate Inhibitor Test 1 Test 2 Test 1 Test 2 (mpy) Baseline16.1143 16.3113 16.1066 16.3037 0.36 solution only 5% Blend of 16.529116.7320 16.5247 16.7260 0.24 turpentine liquids 10% Blend of 17.012817.0229 17.0066 17.0172 0.28 turpentine liquids 15% Blend of 17.107616.4431 17.1056 16.4412 0.09 turpentine liquids

Example 30

The extracting ability of a surfactant free blend of turpentine liquidswas compared to d-limonene containing 0, 3, 9, and 12% surfactant(Surfonic N-95 from Huntsman). The surfactant free blend of turpentineliquids and d-limonene with surfactant were contacted with 30 g of SuperPave Asphalt (weight of aggregate: 92.9%, weight of asphalt: 6.6%,weight of polymer: 0.5%) for two minutes, at a 1:1 ratio of liquid toasphalt at 45° C. The amount of asphalt recovery for the surfactant freeblend of turpentine liquids was 8.3%, while the d-limonene recoveredonly 4%, 6.3%, 5.3%, and 5.7% asphalt at 0, 3, 9, and 12% surfactant,respectively. The surfactant-free blend of turpentine liquids extractedmore hydrocarbon-containing organic matter from asphalt than d-limonenewith or without surfactant.

The results for the extraction of hydrocarbon-containing organic matterfrom hydrocarbon-containing material described in the specification, andespecially in the Examples above, were unexpected.

As measured herein, the recovery, i.e., yield, in certain samplesexceeds 100% because certain hydrocarbon-containing materials, e.g. tarsands, comprise heterogeneous and impure mixtures of exceedingly viscousliquid and relatively coarse solid particles, irregular in shape andvarying in size. Thus, recovery measurements based on the average valueof hydrocarbon matter in the hydrocarbon-containing materials at timesexceed 100% due to these naturally variable factors. Further, someexperimental errors are inherent to any experiment.

As used herein, the terms about and approximately should be interpretedto include any values which are within 5% of the recited value.Furthermore, recitation of the term about and approximately with respectto a range of values should be interpreted to include both the upper andlower end of the recited range. As used herein, the terms first, second,third and the like should be interpreted to uniquely identify elementsand do not imply or restrict to any particular sequencing of elements orsteps.

While the invention has been shown or described in only some of itsembodiments, it should be apparent to those skilled in the art that itis not so limited, but is susceptible to various changes withoutdeparting from the scope of the invention.

1. A method for increasing recovery of hydrocarbon-containing organicmatter from a production well coupled to a hydrocarbon-containingsub-surface formation, the subsurface formation comprisinghydrocarbon-containing material, the method comprising the steps ofextracting the hydrocarbon-containing organic matter by a processcomprising: providing an injection well, said injection being in fluidcommunication with the sub-surface formation; providing a substantiallysurfactant-free first liquid comprising non-aqueoushydrocarbon-extracting turpentine liquid; injecting the non-aqueoushydrocarbon-extracting turpentine liquid through the injection well andinto the formation, wherein the non-aqueous hydrocarbon-extractingturpentine liquid and the hydrocarbon-containing organic matter from thehydrocarbon containing sub-surface formation form an extraction mixturecomprising at least a portion of the hydrocarbon-containing organicmatter extracted into the non-aqueous hydrocarbon-extracting turpentineliquid; recovering the extraction mixture from the formation through theproduction well; and separating the extraction mixture to produce ahydrocarbon product stream and a hydrocarbon-extracting liquid stream.2. The method of claim 1, wherein said non-aqueoushydrocarbon-extracting turpentine liquid is selected from the groupconsisting of natural turpentine, synthetic turpentine, mineralturpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol,γ-terpineol, terpene resins, α-terpene, β-terpene, γ-terpene, geraniol,3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinanehydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol,p-menthan-8-ol, α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.
 3. The method of claim 1, wherein saidcontacting comprises mixing.
 4. The method of claim 1, wherein thenon-aqueous hydrocarbon-extracting turpentine liquid comprises at leastabout 30% by volume α-terpineol and at least about 15% pinene.
 5. Themethod of claim 1, wherein the non-aqueous hydrocarbon-extractingturpentine liquid comprises at least about 50% by volume α-terpineol andat least about 20% by volume α- and/or β-pinene.
 6. The method of claim5, wherein the non-aqueous hydrocarbon-extracting turpentine liquidfurther comprises at least one of α-terpene, β-terpene or γ-terpene. 7.The method of claim 1, wherein the non-aqueous hydrocarbon-extractingturpentine liquid comprises α-terpineol and β-terpineol, wherein theratio of α-terpineol to β-terpineol is at least about 1.3:1.
 8. Themethod of claim 1, wherein the non-aqueous hydrocarbon-extractingturpentine liquid comprises α-terpineol and β-terpineol, wherein theratio of α-terpineol to α- and/or β-pinene is at least about 2:1.
 9. Themethod of claim 1, wherein the non-aqueous hydrocarbon-extractingturpentine liquid consists essentially of a mixture of α-terpineol,β-terpineol, α-terpene, and β-terpene.
 10. The method of claim 1,wherein the non-aqueous hydrocarbon-extracting turpentine liquidconsists essentially of a mixture of α-terpineol, and α- and/orβ-pinene.
 11. The method of claim 1, wherein the non-aqueoushydrocarbon-extracting turpentine liquid consists essentially of: about40-60% α-terpineol, pine oil, about 5-20% β-pinene, and about 0-10%p-cymene.
 12. The method of claim 11, wherein said non-aqueoushydrocarbon-extracting turpentine liquid contains about 5% p-cymene. 13.The method of claim 1, wherein the non-aqueous hydrocarbon-extractingturpentine liquid consists essentially of: about 40-60% α-terpineol,about 5-10% α-pinene, about 5-20% β-pinene, and about 0-10% p-cymene.14. A method of modifying sulfur compounds in a sulfur-containinghydrocarbon-containing material from a natural geological formationcomprising the steps of: providing a substantially surfactant-free firstliquid comprising a non-aqueous liquid consisting essentially of aturpentine liquid selected from the group consisting of naturalturpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof, and contacting the sulfur-containinghydrocarbon-containing material from a natural geological formation withsaid non-aqueous liquid so as to interact with sulfur in saidsulfur-containing hydrocarbon-containing material from a naturalgeological formation and thereby modify said sulfur-containinghydrocarbon-containing material from a natural geological formation;wherein said sulfur-containing hydrocarbon-containing material from anatural geological formation is selected from the group consisting ofnatural gas, petroleum gas, crude oil, tar sands, oil shale, and coal.15. The method of claim 13, wherein said sulfur-containinghydrocarbon-containing material from a natural geological formationcontains elemental sulfur, hydrogen sulfide, sulfides, disulfides,mercaptans, thiophenes, and/or benzothiophenes.
 16. The method of claim13, further comprising bubbling natural gas or petroleum gas throughsaid non-aqueous liquid.
 17. A composition consisting essentially of ahydrocarbon-extracting effective amount of α-terpineol, β-terpineol,β-pinene, α-pinene, pine oil, p-cymene, or a combination thereof. 18.The composition of claim 16, wherein said composition consistsessentially of: about 40-60% α-terpineol, pine oil, about 5-20%β-pinene, and about 0-10% p-cymene.
 19. The composition of claim 17,wherein said composition contains about 5% p-cymene.
 20. The compositionof claim 16, wherein said composition consists essentially of about40-60% α-terpineol, about 30-40% α-pinene, about 5-20% β-pinene, andabout 0-10% p-cymene.
 21. The composition of claim 19, wherein saidcomposition contains about 5% p-cymene.